US20180134842A1 - Resin composition, prepreg, laminate and multilayer printed wiring board - Google Patents
Resin composition, prepreg, laminate and multilayer printed wiring board Download PDFInfo
- Publication number
- US20180134842A1 US20180134842A1 US15/570,215 US201615570215A US2018134842A1 US 20180134842 A1 US20180134842 A1 US 20180134842A1 US 201615570215 A US201615570215 A US 201615570215A US 2018134842 A1 US2018134842 A1 US 2018134842A1
- Authority
- US
- United States
- Prior art keywords
- group
- resin composition
- mass
- carbon atoms
- polyphenylene ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 127
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 157
- -1 N-substituted maleimide structure Chemical group 0.000 claims abstract description 130
- 150000002170 ethers Chemical class 0.000 claims abstract description 101
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 88
- 239000003822 epoxy resin Substances 0.000 claims abstract description 61
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 61
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000011347 resin Substances 0.000 claims abstract description 51
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 50
- 125000005843 halogen group Chemical group 0.000 claims abstract description 36
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 25
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 claims abstract description 15
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 82
- 239000003063 flame retardant Substances 0.000 claims description 49
- 239000003960 organic solvent Substances 0.000 claims description 49
- 229910052751 metal Inorganic materials 0.000 claims description 38
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 33
- 239000011256 inorganic filler Substances 0.000 claims description 28
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 28
- 125000002947 alkylene group Chemical group 0.000 claims description 23
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims description 15
- 125000001033 ether group Chemical group 0.000 claims description 15
- 125000000468 ketone group Chemical group 0.000 claims description 15
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 15
- 125000000101 thioether group Chemical group 0.000 claims description 15
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 14
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 14
- 125000001118 alkylidene group Chemical group 0.000 claims description 12
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000005567 fluorenylene group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 abstract description 49
- 239000004020 conductor Substances 0.000 abstract description 35
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract description 6
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 106
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 58
- 238000004519 manufacturing process Methods 0.000 description 55
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 51
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 239000011889 copper foil Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 21
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 20
- 239000007809 chemical reaction catalyst Substances 0.000 description 20
- 229910052698 phosphorus Inorganic materials 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 20
- 229920003192 poly(bis maleimide) Polymers 0.000 description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 238000005476 soldering Methods 0.000 description 17
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 16
- 239000011574 phosphorus Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 14
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 13
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- GNQAGTIQCCWTSZ-UHFFFAOYSA-N aluminum;diethylphosphinic acid Chemical compound [Al].CCP(O)(=O)CC GNQAGTIQCCWTSZ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007822 coupling agent Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 10
- 101100273797 Caenorhabditis elegans pct-1 gene Proteins 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000000935 solvent evaporation Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 150000001913 cyanates Chemical class 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 239000000806 elastomer Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229920001169 thermoplastic Polymers 0.000 description 9
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 8
- KWOIWTRRPFHBSI-UHFFFAOYSA-N 4-[2-[3-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=CC(C(C)(C)C=2C=CC(N)=CC=2)=CC=1C(C)(C)C1=CC=C(N)C=C1 KWOIWTRRPFHBSI-UHFFFAOYSA-N 0.000 description 8
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 238000006845 Michael addition reaction Methods 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 239000004416 thermosoftening plastic Substances 0.000 description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 7
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 150000007942 carboxylates Chemical class 0.000 description 7
- 150000002460 imidazoles Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 229930185605 Bisphenol Natural products 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- UOBLPIXDROQEKY-UHFFFAOYSA-N CC.CC.CC1=CC=CC=C1.CC1=CC=CC=C1.CCC Chemical compound CC.CC.CC1=CC=CC=C1.CC1=CC=CC=C1.CCC UOBLPIXDROQEKY-UHFFFAOYSA-N 0.000 description 6
- JQVBISUYNZCEAG-UHFFFAOYSA-N CC.CC.CCC.COC1=CC=CC=C1.COC1=CC=CC=C1 Chemical compound CC.CC.CCC.COC1=CC=CC=C1.COC1=CC=CC=C1 JQVBISUYNZCEAG-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 150000001451 organic peroxides Chemical class 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 229940018563 3-aminophenol Drugs 0.000 description 5
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
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- XQCDLHVXAXBMGW-UHFFFAOYSA-N 1-[6-(2,5-dioxopyrrol-1-yl)-3,5,5-trimethylhexyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC(C)(C)CC(C)CCN1C(=O)C=CC1=O XQCDLHVXAXBMGW-UHFFFAOYSA-N 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
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- 125000000217 alkyl group Chemical group 0.000 description 4
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- ZCVKUGQKEHYZJW-UHFFFAOYSA-N phenol;4-(2-phenylpropan-2-yl)phenol Chemical compound OC1=CC=CC=C1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 ZCVKUGQKEHYZJW-UHFFFAOYSA-N 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- ABMSPIUYLYKRLM-UHFFFAOYSA-N styrene hydrobromide Chemical compound Br.C=CC1=CC=CC=C1 ABMSPIUYLYKRLM-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
- C08G73/127—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to a resin composition containing a polyphenylene ether derivative, and to a prepreg, a laminate and a multilayer printed wiring board.
- Signals used in mobile communication devices such as a cell phone, base station apparatuses for them, network infrastructure devices, such as a server and a router, large-sized computers, and the like are being increased in the speed and capacity.
- printed wiring boards mounted on these electronic devices are required to adapt to high-frequency signals, and a substrate material having excellent dielectric characteristics (low dielectric constant and low dielectric dissipation factor; hereinafter these may be referred to as high frequency properties) in a high frequency range that enable reduction of a transmission loss is demanded.
- a polyphenylene ether (PPE) resin has been used as a heat-resistant thermoplastic polymer excellent in high frequency properties.
- PPE polyphenylene ether
- a method of using a polyphenylene ether and a thermosetting resin as combined has been proposed.
- a resin composition containing a polyphenylene ether and an epoxy resin see, for example, PTL 1
- a resin composition using a polyphenylene ether in connection with a cyanate ester resin having a low dielectric constant among thermosetting resins see, for example, PTL 2 and the like have been disclosed.
- the resin compositions described in the above-mentioned PTL's 1 and 2 are unsatisfactory collectively in the high frequency properties in a GHz region, the adhesion to conductor, the low thermal expansion coefficient, and the flame retardancy.
- the compatibility of polyphenylene ether with a thermosetting resin is low, and therefore the heat resistance of the resultant resin composition may often lower.
- the present inventors have proposed a resin composition having a polyphenylene ether resin and a polybutadiene resin as a base, wherein the resin composition can be improved in the compatibility, heat resistance, low thermal expansion coefficient, adhesion to conductor, and the like by performing semi-IPN (semi-interpenetrating network) formation in the production stage (A-stage) of producing a resin composition containing an organic solvent (for example, PTL 3).
- semi-IPN semi-interpenetrating network
- the substrate material recently used for a printed wiring board is not only required to adapt to high-frequency signals, but also required to have high adhesion to conductor, low thermal expansion coefficient, high glass transition temperature, high flame retardancy, and the like due to the demands for an increase in the density, high reliability, and adaptability to consideration of the environment.
- the adhesion to conductor is desired to be 0.6 kN/m or more, in terms of a copper foil peel strength as measured using a low profile copper foil (Rz: 1 to 2 ⁇ m) having a very small surface roughness on the side to be bonded to resin.
- the substrate material for printed wiring board used in the application of network related devices is needed to be stacked into the increased number of layers as the density of the wiring board is increased, and therefore the substrate material is required to have high reflow heat resistance and through-hole reliability.
- the glass transition temperature of the material as a yardstick for the above properties is desirably 200° C. or higher, and the thermal expansion coefficient (in the Z-direction at the Tg or lower) is desirably 45 ppm/° C. or less, further desirably 40 ppm/° C. or less.
- the incorporation of an inorganic filler into the resin composition is effective; however, in a multilayer printed wiring board with the increased number of layers, for surely obtaining the flow properties of the resin for circuit packing, the amount of the inorganic filler to be incorporated is restricted. Therefore, it is desired that even when the amount of the inorganic filler incorporated is relatively small, the resultant resin composition is desired to secure the above-mentioned required values.
- a substrate material using an ordinary E glass substrate is desired to have a dielectric constant of 3.8 or less, more desirably 3.7 or less, and even more desirably 3.6 or less, and to have an dielectric dissipation factor of 0.007 or less, more desirably 0.006 or less.
- a substrate material generally tends to have an increased dielectric dissipation factor at a higher frequency, but is increasingly strongly needed to satisfy the above-mentioned required values in a 10 GHz or more band which is a frequency band higher than the conventional 1 to 5 GHz band for the dielectric properties values.
- an object of the present invention is to provide a resin composition having especially excellent compatibility and having good dielectric properties in a high frequency range (low dielectric constant and low dielectric dissipation factor), high adhesion to conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient, and high flame retardancy, and to provide a prepreg, a laminate, and a multilayer printed wiring board using the resin composition.
- the present inventors have conducted extensive and intensive studies with a view toward solving the above-mentioned problems. As a result, the inventors have found that a prepreg and a laminate using a resin composition that contains a polyphenylene ether derivative having a specific molecular structure, a specific thermosetting resin and a styrenic thermoplastic elastomer can express excellent high frequency properties, high heat resistance, high adhesion to conductors, high glass transition temperature, low thermal expansion coefficient and high flame retardancy, and have completed the present invention.
- the present invention relates to the following [1] to [16].
- thermosetting resin selected from the group consisting of an epoxy resin, a cyanate resin and a maleimide compound
- thermoplastic elastomer (C) a styrenic thermoplastic elastomer
- R 1 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and x represents an integer of 0 to 4.
- R 2 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom
- y represents an integer of 0 to 4
- a 1 represents a group represented by the following general formula (II), (III), (IV) or (V):
- R 3 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, p represents an integer of 0 to 4:
- R 4 and R 5 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom
- a 2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a group represented by the following general formula (III-1)
- q and r each independently represent an integer of 0 to 4:
- R 6 and R 7 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom
- a 3 represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond
- s and t each independently represent an integer of 0 to 4:
- n an integer of 0 to 10:
- R 8 and R 9 each independently represent a hydrogen atom, or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and u represents an integer of 1 to 8.
- a 4 has the same definition as that of A 1 in the general formula (Z)
- a 5 represents a group represented by the following general formula (VII):
- R 17 and R 18 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom
- a 8 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or a group represented by the following general formula (VII-1) or (VII-2), and q′ and r′ each independently represent an integer of 0 to 4:
- R 19 and R 20 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom
- a 9 represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond
- s′ and t′ each independently represent an integer of 0 to 4:
- R 21 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom
- a 10 and A 11 each independently represent an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond
- w represents an integer of 0 to 4.
- the resin composition of the present invention has particularly good compatibility, excellent high frequency properties (low dielectric constant, low dielectric dissipation factor), high adhesion to conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient and high flame retardancy. Accordingly, the prepreg and the laminate to be obtained using the resin composition can be favorably used for electronic parts such as multilayer printed wiring boards, etc.
- One aspect of the present invention is a resin composition containing:
- polyphenylene ether derivative (A) a polyphenylene ether derivative having an N-substituted maleimide structure-containing group and a structural unit represented by the following general formula (I) in one molecule [hereinafter this may be simply abbreviated as polyphenylene ether derivative (A) or component (A)],
- thermosetting resin (B) at least one thermosetting resin selected from the group consisting of an epoxy resin, a cyanate resin and a maleimide compound [hereinafter this may be simply abbreviated as thermosetting resin (B) or component (B)], and
- component (C) a styrenic thermoplastic elastomer [hereinafter this may be abbreviated as component (C)].
- R 1 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, x represents an integer of 0 to 4.
- the polyphenylene ether derivative (A) has an N-substituted maleimide structure-containing group and a structural unit represented by the above-mentioned general formula (I) in one molecule.
- the resin composition can have excellent high frequency properties (low dielectric constant, low dielectric dissipation factor), high adhesion to conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient and high flame retardancy.
- the thermal expansion coefficient as referred to in the present invention means a value also called a linear expansion coefficient.
- R 1 in the general formula (I) each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom.
- the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc.
- the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and may be a methyl group.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.
- R 1 may be an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
- x is an integer of 0 to 4, and may be an integer of 0 to 2, and may 2.
- R 1 may be substituted at the ortho-position on the benzene ring (based on the substitution position of the oxygen atom).
- plural R 1 's may be the same or different.
- the structural unit represented by the general formula (I) may be a structural formula represented by the following general formula (I′).
- the N-substituted maleimide structure-containing group that the polyphenylene ether derivative (A) has may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy, a group containing a bismaleimide structure in which the nitrogen atoms of the two maleimide groups bond to each other via an organic group, and may be a group represented by the following general formula (Z).
- R 2 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom
- y represents an integer of 0 to 4
- a 1 represents a group represented by the following general formula (II), (III), (IV) or (V).
- the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R 2 represents may be described in the same manner as that for the case of R 1 .
- y is an integer of 0 to 4, and may be an integer of 0 to 2, and may be 0.
- y is an integer of 2 or more, plural R 2 's may be the same or different.
- R 3 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, p represents an integer of 0 to 4.
- the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R 3 represents may be described in the same manner as that for the case of R 1 .
- p is an integer of 0 to 4, and, from the viewpoint of easy availability, may be an integer of 0 to 2, or 0 or 1, or 0.
- p is an integer of 2 or more, plural R 3 's may be the same or different.
- R 4 and R 5 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom
- a 2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a group represented by the following general formula (III-1)
- q and r each independently represent an integer of 0 to 4.
- the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R 4 and R 5 represent include the same ones as those for R 1 .
- the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and may be a methyl group or an ethyl group, and may be an ethyl group.
- Examples of the alkylene group having 1 to 5 carbon atoms that A 2 represents include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc.
- the alkylene group may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy, an alkylene group having 1 to 3 carbon atoms, or may be a methylene group.
- Examples of the alkylidene group having 2 to 5 carbon atoms that A 2 represents include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc.
- it may be an isopropylidene group.
- a 2 may be an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.
- q and r each are independently an integer of 0 to 4, and, from the viewpoint of easy availability, may be an integer of 0 to 2, or 0 or 2.
- q or r is an integer of 2 or more, plural R 4 's or plural R 5 's each may be the same or different.
- R 6 and R 7 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom
- a 3 represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond
- s and t each independently represent an integer of 0 to 4.
- the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R 6 and R 7 represent may be described in the same manner as that for the case of R 4 and R 5 .
- the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms that A 3 represents include the same ones as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms that A 2 represents.
- the alkylidene group having 2 to 5 carbon atoms may be selected for A 3 .
- s and t each are independently an integer of 0 to 4, and, from the viewpoint of easy availability, may be an integer of 0 to 2, or may be 0 or 1, or may be 0.
- s or t is an integer of 2 or more, plural R 6 's or plural R 7 's each may be the same or different.
- n represents an integer of 0 to 10.
- n may be an integer of 0 to 5, or may be an integer of 0 to 3.
- R 8 and R 9 each independently represent a hydrogen atom, or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, u represents an integer of 1 to 8.
- the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R 8 and R 9 represent may be described in the same manner as that for the case of R 1 .
- u is an integer of 1 to 8, and may be an integer of 1 to 3, or may be 1.
- a 1 in the group represented by the general formula (Z) may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy, a group represented by any of the following formulae.
- the polyphenylene ether derivative (A) may be a polyphenylene ether derivative represented by the following general formula (A′).
- a 1 , R 1 , R 2 , x and y are as defined hereinabove, m represents an integer of 1 or more.
- m may be an integer of 1 to 300, or may be an integer of 10 to 300, or may be an integer of 30 to 200, or may be an integer of 50 to 150.
- the polyphenylene ether derivative (A) may be a polyphenylene ether derivative represented by any of the following formulae.
- the derivative may be a polyphenylene ether derivative of the above formula (A′-1), from the viewpoint of excellent dielectric properties and low water absorbability, it may be a polyphenylene ether derivative represented by the formula (A′-2), and from the viewpoint of excellent adhesion to conductor and mechanical properties (elongation, strength at break, etc.), it may be a polyphenylene ether derivative represented by the formula (A′-3). Accordingly, in conformity to the intended properties, one alone or two or more of the polyphenylene ether derivatives of the formulae (A′-1) to (A′-3) may be used either singly or as combined.
- the number average molecular weight of the polyphenylene ether derivative (A) of the present invention may be 5,000 to 12,000, or may be 7,000 to 12,000, or may be 7,000 to 10,000.
- the resin composition of the present invention and the prepreg and the laminate using the composition tend to have a more favorable glass transition temperature.
- the number average molecular weight is 12,000 or less, the resin composition of the present invention tend to be readily molded into a laminate with better formability.
- the number average molecular weight is a value calculated based on the calibration curve drawn using a standard polystyrene, according to gel permeation chromatography (GPC), and more precisely, a value measured according to the number average molecular weight measurement method described in the section of Examples.
- GPC gel permeation chromatography
- the polyphenylene ether derivative (A) may be obtained, for example, according to the production method mentioned below.
- an aminophenol compound represented by the following general formula (VIII) [hereinafter referred to as aminophenol compound (VIII)] is reacted with a polyphenylene ether having, for example, a number average molecular weight of 15,000 to 25,000 in an organic solvent in a mode of known redistribution reaction, as associated with reduction in the polyphenylene ether, to thereby produce a polyphenylene ether compound having a primary amino group in one molecule (A′′) (hereinafter this may be simply referred to as polyphenylene ether compound (A′′)), and then the polyphenylene ether compound (A′′) is reacted with a bismaleimide compound represented by the general formula (IX) [hereinafter referred to as bismaleimide compound (IX)] in a mode of Michael addition reaction to produce the polyphenylene ether derivative (A).
- a bismaleimide compound represented by the general formula (IX) hereinafter referred to as bismaleimide compound (IX)] in a
- a 1 is the same as in the general formula (I).
- aminophenol compound (VIII) examples include o-aminophenol, m-aminophenol, p-aminophenol, etc.
- the compound may be m-aminophenol or p-aminophenol, or may be p-aminophenol.
- the molecular weight of the polyphenylene ether compound (A′′) may be controlled by the amount to be used of the aminophenol compound (VIII), and when the amount of the aminophenol compound (VIII) used is larger, the molecular weight of the polyphenylene ether compound (A′′) is lower. Namely, the amount to be used of the aminophenol compound (VIII) may be adequately controlled so that the number average molecular weight of the polyphenylene ether derivative (A) to be produced finally could fall within a preferred range.
- the amount to be incorporated of the aminophenol compound (VIII) is not specifically limited, but for example, when the number average molecular weight of the polyphenylene ether to be reacted with the aminophenol compound (VIII) is 15,000 to 25,000, the amount may fall within a range of 0.5 to 6 parts by mass relative to 100 parts by mass of the polyphenylene ether to give a polyphenylene ether derivative (A) having a number average molecular weight of 5,000 to 12,000.
- Examples of the organic solvent for use in the production step for the polyphenylene ether compound (A′′) include, though not specifically limited thereto, alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; aromatic hydrocarbons such as toluene, xylene, mesitylene, etc.; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate, etc.; nitrogen-containing compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. One alone or two or more kinds of these may be used either singly or as combined.
- a reaction catalyst may be used as needed.
- the reaction catalyst in redistribution reaction is applicable.
- an organic peroxide such as t-butylperoxyisopropyl monocarbonate or the like and a metal carboxylate such as manganese naphthenate or the like may be used as combined.
- the amount of the reaction catalyst to be used is not specifically limited.
- the amount of the organic peroxide may be 0.5 to 5 parts by mass and that of the metal carboxylate may be 0.05 to 0.5 parts by mass relative to 100 parts by mass of the polyphenylene ether to be reacted with the aminophenol compound (VIII).
- the aminophenol compound (VIII), the polyphenylene ether having a number average molecular weight of 15,000 to 25,000, an organic solvent and optionally a reaction catalyst are put in a reactor each in a predetermined amount, and reacted with heating, keeping the heat and stirring to give the polyphenylene ether compound (A′′).
- the reaction temperature and the reaction time in this step the reaction conditions in known redistribution reaction are applicable.
- the reaction may be carried out at a reaction temperature of 70 to 110° C. and for a reaction time of 1 to 8 hours.
- a solution of the polyphenylene ether compound (A′′) thus produced in the manner as above may be continuously and directly fed to the next step of producing the polyphenylene ether derivative (A).
- the solution of the polyphenylene ether compound (A′′) may be cooled, or may be controlled to be at the reaction temperature in the next step.
- the solution may be concentrated to remove a part of the organic solvent, or may be diluted by adding an organic solvent thereto, as described below.
- Examples of the bismaleimide compound (IX) to be used in producing the polyphenylene ether derivative (A) include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(4-maleimidophenyl) sulfone, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) ketone, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(4-(4-
- bis(4-maleimidophenyl)methane 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane may be selected.
- Bis(4-maleimidophenyl)methane may be used because the polyphenylene ether derivative containing the formula (A′-1) above is obtained and it is inexpensive.
- 3,3′-Dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide may be used because the polyphenylene ether derivative containing the formula (A′-2) above is obtained and exhibits excellent dielectric properties and low water absorption properties.
- 2,2-Bis(4-(4-maleimidophenoxy)phenyl)propane may be used because the polyphenylene ether derivative containing the formula (A′-3) above is obtained and exhibits high adhesion to conductor and excellent mechanical properties (elongation, strength at break).
- the amount of the bismaleimide compound (IX) is determined according to the amount of the aminophenol compound (VIII) used. Specifically, the bismaleimide compound may be incorporated so that the equivalent ratio (Tb1/Ta1) of the maleimide group equivalent (Tb1) of the bismaleimide compound (IX) to the —NH 2 group equivalent (Ta1) of the aminophenol compound (VIII) could be in the range of 2 to 6, or in a rage of 2 to 4.
- the resin composition, the prepreg and the laminate of the present invention tend to have more excellent heat resistance, high glass transition temperature and high flame retardancy.
- a reaction catalyst may be used as needed.
- the reaction catalyst used there is no particular limitation.
- the reaction catalyst include acidic catalysts, such as p-toluenesulfonic acid; amines, such as triethylamine, pyridine, and tributylamine; imidazole compounds, such as methylimidazole and phenylimidazole; and phosphorus catalysts, such as triphenylphosphine. These may be used individually or in combination.
- the amount of the reaction catalyst incorporated there is no particular limitation. However, for example, relative to 100 parts by mass of the polyphenylene ether compound (A′′), the reaction catalyst can be used in an amount in the range of 0.01 to 5 parts by mass.
- the bismaleimide compound (IX) and optionally a reaction catalyst and others are put into the solution of the polyphenylene ether compound (A′′) solution each in a predetermined amount, and reacted with heating, keeping the heat and stirring in a mode of Michael reaction to give the polyphenylene ether derivative (A).
- the reaction temperature may be 50 to 160° C.
- the reaction time may be 1 to 10 hours.
- an organic solvent may be added, or the reaction system may be concentrated as mentioned above, to thereby control the reaction concentration (solid concentration, and the solution viscosity.
- the organic solvents exemplified in the section of the production step for the polyphenylene ether compound (A′′) are applicable, and one alone or two or more kinds of these may be used either singly or as combined.
- methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N,N-dimethylformamide and N,N-dimethylacetamide may be selected.
- the reaction concentration (solid concentration) in the production step for the polyphenylene ether derivative (A) and the polyphenylene ether (A′′) is not specifically limited, but, for example, in each production step, the concentration may be 10 to 60% by mass, and may be 20 to 50% by mass.
- the reaction concentration is 10% by mass or more, the reaction speed is not too low, and tends to be favorable from the viewpoint of production cost.
- the reaction concentration is 60% by mass or less, better solubility tends to be attained. If so, in addition, the solution viscosity may be low and the stirring efficiency tends to be good to suppress gelation.
- a part or all of the organic solvent may be optionally removed from the solution for concentration, or an additional organic solvent may be added thereto for dilution, in accordance with the operability in taking out the derivative from the reactor or with the use condition (for example, solution viscosity or solution concentration suitable for production of prepreg) in preparing the resin composition of the present invention by adding various thermosetting resins to the polyphenylene ether derivative (A).
- the additional organic solvent is not specifically limited, and one or more organic solvents mentioned above may be used.
- the formation of the polyphenylene ether compound (A′′) and the polyphenylene ether derivative (A) in the above-mentioned production steps may be confirmed through GPC and IR analysis by sampling a small amount of the product after each step.
- the production of a desired polyphenylene ether compound (A′′) can be confirmed by GPC showing that the molecular weight is reduced to be lower than the polyphenylene ether having a number average molecular weight of 15,000 to 25,000 and that the peak of the aminophenol compound (VIII) as a raw material has disappeared, and by IR analysis showing that a peak of the primary amino group appears at 3,300 to 3,500 cm ⁇ 1 .
- the resin composition of the present invention tends to be more excellent in adhesion to conductor, heat resistance, thermal expansion coefficient, flame retardancy and workability (in drilling, cutting) than the resin composition containing the polyphenylene ether compound (A′′) and the component (B) to be mentioned below.
- the resin component (B) contained in the resin composition of the present invention is at least one thermosetting resin selected from the group consisting of an epoxy resin, a cyanate resin and a maleimide compound.
- the maleimide compound does not include the above-mentioned polyphenylene ether derivative (A).
- the component (B) may be at least one thermosetting resin selected from the group consisting of an epoxy resins and a maleimide compound.
- the epoxy resin may be an epoxy resin having two or more epoxy groups in one molecule.
- the epoxy resin is grouped into a glycidyl ether-type epoxy resin, a glycidylamine-type epoxy resin, a glycidyl ester-type epoxy resin, etc.
- a glycidyl ether-type epoxy resin may be selected.
- the epoxy resin is grouped into various types of epoxy resins depending on the difference in the main skeleton, and various types of the epoxy resins mentioned above may be further grouped into a bisphenol-type epoxy resin such as a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, etc.; an alicyclic epoxy resin; an aliphatic linear epoxy resin; a novolak-type epoxy resin such as a phenol-novolak-type epoxy resin, a cresol-novolak-type epoxy resin, a bisphenol A-novolak-type epoxy resin, a bisphenol F-novolak-type epoxy resin, etc.; a phenol-aralkyl-type epoxy resin, a stilbene-type epoxy resin, a dicyclopentadiene-type epoxy resin, a naphthalene skeleton-containing epoxy resin such as a naphthol-novolak-type epoxy resin, a naphthol-aralkyl-
- One alone or two or more kinds of epoxy resins may be used either singly or as combined.
- a naphthalene skeleton-containing epoxy resin and a biphenylaralkyl-type epoxy resin may be used.
- a curing agent or a curing aid for epoxy resin may be used as combined.
- these include, though not specifically limited thereto, polyamine compounds such as diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, m-phenylenediamine, dicyandiamide, etc.; polyphenol compounds such as bisphenol A, phenol-novolak resin, cresol-novolak resin, bisphenol A-novolak resin, phenolaralkyl resin, etc.; acid anhydrides such as phthalic anhydride, pyromellitic anhydride, etc.; carboxylic acid compounds; active ester compounds, etc.
- One alone or two or more of these may be used either singly or as combined.
- the amount thereof to be used is not specifically limited and may be adequately controlled depending on the object.
- polyphenol compounds and active ester compounds may be used.
- cyanate resin examples include, though not specifically limited thereto, 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)ethane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, ⁇ , ⁇ ′-bis(4-cyanatophenyl)-m-diisopropylbenzene, cyanate ester compound of phenol-added dicyclopentadiene polymer, phenol-novolak-type cyanate ester compound and cresol-novolak-type cyanate ester compound.
- One alone or two or more kinds of cyanate resins may be used either singly or as combined.
- 2,2-bis(4-cyanatophenyl)propane may be used.
- a curing agent or a curing aid for cyanate resin may be used as combined.
- these include, though not specifically limited thereto, monophenol compounds, polyphenol compounds, amine compounds, alcohol compounds, acid anhydrides, carboxylic acid compounds, etc. One alone or two or more of these may be used either singly or as combined.
- the amount of the curing agent and the curing aid to be used is not specifically limited and may be adequately controlled depending on the object. Among these, from the viewpoint of high frequency properties, heat resistance, moisture absorption resistance and storage stability, monophenol compounds may be used.
- a method of pre-reacting them to give a phenol-modified cyanate prepolymer may be employed.
- the monophenol compound to be used in combination all the prescribed amount thereof may be incorporated in prepolymerization, or the prescribed amount may be divided in portions and added portionwise before and after prepolymerization, but from the viewpoint of storage stability, the method of portionwise incorporating the compound may be employed.
- the maleimide compound is not specifically limited, but, for example, at least one of (a) a polymaleimide compound having at least two N-substituted maleimide groups in one molecule [hereinafter this may be referred to as component (a)] and (c) a polyaminobismaleimide compound represented by the following general formula (VI) [hereinafter this may be referred to as component (c)] may be contained.
- the maleimide compound may be the polyaminobismaleimide compound (c).
- the polyaminobismaleimide compound (c) may be obtained, for example, by reacting the component (a) and an aromatic diamine compound (b) having two primary amino groups in one molecule [hereinafter this may be referred to as component (b)] in a mode of Michael addition reaction in an organic solvent:
- a 4 has the same definition as A 1 in the above general formula (Z), and A 5 is a group represented by the following general formula (VII):
- R 17 and R 18 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom
- a 8 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or a group represented by the following general formula (VII-1) or (VII-2), and q′ and r′ each independently represent an integer of 0 to 4:
- R 19 and R 20 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom
- a 9 represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond
- s′ and t′ each independently represent an integer of 0 to 4:
- R 21 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom
- a 10 and A 11 each independently represent an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond
- w represents an integer of 0 to 4.
- the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R 17 , R 18 , R 19 , R 20 and R 21 in the above general formula (VII), (VII-1) or (VII-2) represent include the same ones as those of R 1 in the general formula (I).
- the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and may be a methyl group or an ethyl group.
- a 4 in the general formula (VI) have the same definition as A 1 in the general formula (Z).
- the alkylene group having 1 to 5 carbon atoms that A 8 and A 9 in the above general formula (VII), (VII-1) or (VII-2) represent, and the alkylidene group having 2 to 5 carbon atoms that A 8 represents may be described in the same manner as that for the case of A 2 in the general formula (III).
- the alkylene group having 1 to 5 carbon atoms that A 10 and A 11 in the general formula (VII-2) represent may be described in the same manner as that for the case of A 2 in the general formula (III).
- q′ and r′ each are an integer of 0 to 4, and from the viewpoint of easy availability, both may be an integer of 0 to 2, or may be 0 or 2.
- s′ and t′ each are an integer of 0 to 4, and from the viewpoint of easy availability, both may be an integer of 0 to 2, or may be 0 or 1, or may be 0.
- w is an integer of 0 to 4, and from the viewpoint of easy availability, may be an integer of 0 to 2, or may be 0.
- the component (a) is not specifically limited, but for example, the same ones as those of the above-mentioned bismaleimide compound (IX) are applicable.
- Examples of the component (a) include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(4-maleimidophenyl) sulfone, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) ketone, 2,2-bis(4-(4-maleimi
- the component (a) may be a bismaleimide compound, and may be bis(4-maleimidophenyl)methane from the viewpoint of inexpensiveness, may be 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide from the viewpoint of excellent dielectric properties and low water absorption, and may be 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane from the viewpoint of high adhesion to conductor and excellent mechanical properties (elongation, strength at break).
- the polyaminobismaleimide compound (c) may be obtained by reacting the above component (a) and an aromatic diamine compound (b) having two primary amino groups in one molecule in an organic solvent in a mode of Michael addition reaction.
- component (b) examples include, though not specifically limited thereto, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ketone, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethy
- the component may be selected from 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline, and 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline.
- the component may be 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, or 4,4′-diamino-3,3′-diethyl-diphenylmethane.
- the compound may be 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline, or 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline.
- the component may be selected from 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline and 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline. According to the object and use, these may be used individually or in combination.
- organic solvent used in producing the polyaminobismaleimide compound (c) there is no particular limitation.
- the organic solvents mentioned above as examples in connection with the production step for the polyphenylene ether compound (A′′) can be applied. These may be used individually or in combination. Of these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N,N-dimethylformamide, and N,N-dimethylacetamide may be used from the viewpoint of solubility.
- the component (a) and the component (b) may be incorporated so that the equivalent ratio (Tb2/Ta2) of the maleimide group equivalent (Tb2) of the component (a) to the —NH 2 group equivalent (Ta2) of the component (b) could be in the range of 1 to 10, or could be in the range of 2 to 10.
- the resin composition, the prepreg and the laminate of the present invention can have excellent high frequency properties, high adhesion to conductor, excellent heat resistance, high glass transition temperature and powerful flame retardancy.
- a reaction catalyst may not be used for the Michael addition reaction in producing the polyaminobismaleimide compound (c), but may be used as needed.
- the reaction catalyst is not specifically limited, and the reaction catalyst usable in the Michael addition reaction in producing the above-mentioned polyphenylene ether derivative (A) is applicable. Also as described above, the amount of the reaction catalyst to be incorporated is not specifically limited.
- a curing agent for the maleimide compound may be used.
- these are not specifically limited, and examples thereof include vinyl compounds such as styrene monomer, divinylbenzene, divinylbiphenyl, etc.; (meth)acrylate compounds; allyl compounds such as triallyl cyanurate, triallyl isocyanurate, etc.; polyamine compounds such as diaminodiphenylmethane, etc.
- vinyl compounds or polyamine compounds may be used.
- the above-mentioned component (a) and component (b) and an organic solvent and optionally a reaction catalyst and others are put into a reactor each in a predetermined amount, and with heating, keeping the heat and stirring, these are reacted in a mode of Michael addition reaction to give the polyaminobismaleimide compound (c).
- the reaction conditions in this step for example, the reaction conditions in the Michael addition reaction in producing the above-mentioned polyphenylene ether derivative (A) are applicable.
- the reaction concentration is not specifically limited, but may be 10 to 90% by mass, and may be 20 to 80% by mass.
- the reaction concentration is 10% by mass or more, the reaction speed is not too low, and tends to be advantageous from the viewpoint of production cost.
- the reaction concentration is 90% by mass or less, better solubility tends to be attained. If so, in addition, the solution viscosity may be low and the stirring efficiency tends to be good to suppress gelation.
- a part or all of the organic solvent may be removed (for concentration), or an additional organic solvent may be added for dilution in accordance with the intended object, like in producing the polyphenylene ether derivative (A).
- the content of the component (A) is not specifically limited, but is, from the viewpoint of high frequency properties, preferably 3% by mass or more relative to 100 parts by mass of the sum total of the components (A) to (C), more preferably 5% by mass or more.
- the content of the component (B) is not specifically limited, but is, from the viewpoint of high frequency properties and formability, preferably 10 to 90% by mass relative to 100 parts by mass of the sum total of the components (A) to (C), more preferably 20 to 80% by mass.
- the content ratio of the component (A) to the component (B [(A)/(B)] is not specifically limited, and may be 5/95 to 80/20 by mass, may be 5/95 to 75/25, may be 5/95 to 70/30, and may be 10/90 to 70/30.
- the content ratio of the component (A) to the total content of the component (A) and the component (B) is 5% by mass or more, more excellent high frequency properties and low moisture absorption tend to be attained.
- the ratio is 80% by mass or less, more excellent heat resistance, more excellent formability and more excellent workability tend to be attained.
- the component (C) contained in the resin composition of the present invention is a styrenic thermoplastic elastomer. Containing the component (C), the resin composition of the present invention has good and well-balanced formability, high frequency properties (dielectric properties), adhesion to conductor, soldering heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy.
- R a represents a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms
- R b represents an alkyl group having 1 to 5 carbon atoms
- k represents an integer of 0 to 5.
- Examples of the alkyl group having 1 to 5 carbon atoms that R a and R b represent include a methyl group, an ethyl group, an n-propyl group, etc., and the group may be an alkyl group having 1 to 3 carbon atoms, or may be a methyl group.
- R a may be a hydrogen atom.
- k may be an integer of 0 to 2, or may be 0 or 1, or may be 0.
- the other structural unit than the styrenic compound-derived structural unit that the styrenic thermoplastic elastomer (C) has includes a butadiene-derived structural unit, an isoprene-derived structural unit, a maleic acid-derived structural unit, a maleic anhydride-derived structural unit, etc.
- One alone or two more kinds of styrenic thermoplastic elastomers (C) may be used either singly or as combined.
- the butadiene-derived structural unit and the isoprene-derived structural unit may be hydrogenated.
- the butadiene-derived structural unit is a structural unit of a mixture of an ethylene unit and a butylene unit
- the isoprene-derived structural unit is a structural unit of a mixture of an ethylene unit and a propylene unit.
- the styrenic thermoplastic elastomer (C) may be at least one selected from a styrene-butadiene-styrene block copolymer hydrogenate (SEBS, SBBS), a styrene-isoprene-styrene block copolymer hydrogenate (SEPS) and a styrene-maleic anhydride copolymer (SMA).
- SEBS styrene-butadiene-styrene block copolymer hydrogenate
- SEPS styrene-isoprene-styrene block copolymer hydrogenate
- SMA styrene-maleic anhydride copolymer
- the styrene -butadiene-styrene block copolymer hydrogenate includes SEBS where the hydrogenation ratio of the carbon-carbon double bonds is generally 90% or more (or may be 95% or more), and SBBS where the carbon-carbon double bond at the 1,2-bond site in the butadiene block (see the left side of the following) has been partially hydrogenated (the hydrogenation ratio to all carbon-carbon double bonds is about 60 to 85%).
- the content of the styrene-derived structural unit (hereinafter this may be abbreviated as styrene content) may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature and thermal expansion coefficient, 5 to 80% by mass, or may be 5 to 70% by mass, or may be 10 to 70% by mass, or may be 10 to 50% by mass.
- the melt flow rate (MFR) of SEBS may be, though not specifically limited thereto, 0.1 to 20 g/10 min under the measurement condition at 230° C. and a load of 2.16 kgf (21.2 N), or may be 0.5 to 15 g/10 min.
- SEBS SEBS examples include Tuftec (registered trademark) H Series and M Series manufactured by Asahi Kasei Chemicals Corporation, Septon (registered trademark) Series manufactured by Kuraray Co., Ltd., Crayton (registered trademark) G Polymer Series manufactured by Crayton Polymer Japan Corporation, etc.
- the styrene content in SBBS maybe, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature and thermal expansion, 40 to 80% by mass, or may be 50 to 75% by mass, or may be 55 to 75% by mass.
- the melt flow rate (MFR) of SBBS may be, though not specifically limited thereto, 0.1 to 10 g/10 min under the measurement condition at 190° C. and a load of 2.16 kgf (21.2 N), or maybe 0.5 to 10 g/10 min, or may be 1 to 6 g/10 min.
- SBBS examples of commercial products of SBBS include Tuftec (registered trademark) P Series manufactured by Asahi Kasei Chemicals Corporation, etc.
- the hydrogenation ratio of the styrene-isoprene-styrene block copolymer hydrogenate may be 90% or more, or may be 95% or more.
- the styrene content may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature and thermal expansion, 5 to 60% by mass, or may be 5 to 50% by mass, or may be 10 to 40% by mass.
- the melt flow rate (MFR) of SEPS maybe, though not specifically limited thereto, 0.1 to 130 g/10 min under the measurement condition at 230° C. and a load of 2.16 kgf (21.2 N), or may be 10 to 100 g/10 min, or may be 50 to 90 g/10 min.
- SEPS SEPS
- the styrene content may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature and thermal expansion coefficient, 20 to 90% by mass, or may be 40 to 90% by mass, or may be 50 to 90% by mass, or may be 55 to 85% by mass.
- the maleic anhydride-derived structural unit may be esterified.
- SMA registered trademark
- Resin manufactured by Cray Valley Technology USA, etc.
- thermoplastic elastomers for all the styrenic thermoplastic elastomers (C), commercial products may be used.
- the styrene content and the melt flow rate (MFR) mentioned above are the values described in the manufacturer's catalogue or homepages.
- the content ratio of the component (C) may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature and thermal expansion coefficient, 5 to 60 parts by mass relative to 100 parts by mass of the sum total of the components (A) to (C), or may be 10 to 60 parts by mass, or may be 15 to 60 parts by mass, or may be 15 to 50 parts by mass, or may be 15 to 40 parts by mass.
- the content ratio of the component (C) is 5 parts by mass or more relative to 100 parts by mass of the sum total of the components (A) to (C), high frequency properties and moisture absorption resistance tend to be better, and when 60 parts by mass or less, heat resistance, formability, workability and flame retardancy tend to be better.
- the resin composition of the present invention may contain at least one component selected from an inorganic filler (D) [hereinafter, frequently referred to as “component (D)”], a curing accelerator (E) [hereinafter, frequently referred to as “component (E)”] and a flame retardant (F) [hereinafter, frequently referred to as “component (F)”].
- component (D) inorganic filler
- E curing accelerator
- F flame retardant
- an appropriate inorganic filler (D) optionally incorporated in the resin composition of the present invention can improve low thermal expansion coefficient, high modulus of elasticity, heat resistance and flame retardancy.
- An appropriate curing accelerator (E) incorporated in the resin composition can improve the curability of the resin composition and therefore can improve high frequency properties, heat resistance, adhesion to conductor, modulus of elasticity and glass transition temperature.
- a flame retardant (F) and optionally a flame retardant promoter incorporated in the resin composition can improve the flame retardancy of the composition.
- the component (D) is not specifically limited, but examples thereof include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (calcined clay, etc.), talc, aluminum borate, aluminum borate, silicon carbide, etc. These may be used individually or in combination.
- the component may be silica, alumina, mica or talc, or may be silica or alumina, or maybe silica.
- silica include a precipitated silica produced according to a wet method and having a high water content, and a dry-method silica produced according to a dry method and containing little bound water, and further, the dry-method silica includes ground silica, fumed silica and molten silica (molten spherical silica) as grouped depending on the difference in the production method.
- the particle size may be 0.01 to 20 ⁇ m, or may be 0.1 to 10 ⁇ m.
- the term “particle diameter” used here indicates an average particle diameter, which corresponds to a particle diameter determined at a point of 50% volume in a cumulative frequency distribution curve obtained from the particle diameters when the whole volume of the particles is taken as 100%.
- the particle diameter can be measured by means of a particle size distribution measurement apparatus using a laser diffraction scattering method or the like.
- the content ratio of the component (D) in the resin composition is not specifically limited, but from the viewpoint of thermal expansion coefficient, modulus of elasticity, heat resistance and flame retardancy, the content ratio of the component (D) in the resin composition may be 3 to 65% by volume, or may be 5 to 60%, or may be 15 to 55% by volume.
- the content ratio of the component (D) in the resin composition falls within the above range, better curability, formability and chemical resistance tend to be attained.
- a coupling agent may be used together with it for the purpose of improving the dispersibility of the component (D) and improving the adhesion between the component (D) and the organic component in the resin composition.
- the coupling agent is not specifically limited, and for example, a silane coupling agent or a titanate coupling agent may be adequately selected and used.
- One alone or two or more kinds of coupling agents may be used either singly or as combined.
- the amount of the coupling agent to be used is not also specifically limited, and for example, the amount may be 0.1 to 5 parts by mass relative to 100 parts by mass of the component (D), or may be 0.5 to 3 parts by mass. Within the range, various properties can be prevented from degrading and the characteristics by the use of the component (D) tend to be effectively exhibited.
- a system of using an inorganic filler that has been previously surface-treated in dry or wet with a coupling agent may be employed, but not a so-called integral blending system where the component (D) is first incorporated in the resin composition and then a coupling agent is added thereto.
- Employing the former system promotes effective expression of the characteristics of the component (D).
- the component (D) may be previously dispersed in an organic solvent to be a slurry for the purpose of improving the dispersibility of the component (D) in the resin composition.
- the organic solvent to be used in forming the component (D) into a slurry is not specifically limited, and for example, the organic solvents exemplified hereinabove in the production step for the polyphenylene ether compound (A′′) are applicable. One alone or two or more kinds of these may be used either singly or as combined. Among these, from the viewpoint of dispersibility, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone may be selected.
- the solid content (nonvolatile content) concentration of the slurry is not specifically limited, but for example, from the viewpoint of precipitation and dispersion performance of the inorganic filler (D), the concentration may be 50 to 80% by mass, or may be 60 to 80% by mass.
- a suitable component (E) may be used in accordance with the kind of the component (B) to be used.
- examples of the component (E) include imidazole compounds and derivatives thereof; tertiary mine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenyl phosphine, etc. One alone or two or more kinds of these may be used either singly or as combined. Among these, from the viewpoint of heat resistance, glass transition temperature and storage stability, imidazole compounds and derivatives thereof or phosphorus compounds may be used.
- imidazole compounds include methylimidazole, phenylimidazole, isocyanate-masked imidazole (for example, addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole, etc.) and others, and isocyanate-masked imidazole may be selected.
- Examples of the component (E) in the case where an isocyanate resin is used as the component (B) include imidazole compounds and derivatives thereof; carboxylates with manganese, cobalt, zinc or the like; organic metal compounds such as acetylacetone complexes with a transition metal of manganese, cobalt, zinc or the like, etc. One alone or two or more kinds of these may be used either singly or as combined. Among these, from the viewpoint of heat resistance, glass transition temperature and storage stability, organic metal compounds may be used.
- Examples of the component (E) in the case where a maleimide compound is used as the component (B) include acidic catalysts such as p-toluenesulfonic acid, etc.; amine compounds such as triethylamine, pyridine, tributylamine, etc.; imidazole compounds such as methylimidazole, phenylimidazole, isocyanate-masked imidazole (for example, addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole); tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenyl phosphine, etc.; organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxy
- imidazole compounds from the viewpoint of heat resistance, glass transition temperature and storage stability, imidazole compounds, organic peroxides and carboxylates may be used; or from the viewpoint of heat resistance, glass transition temperature, modulus of elasticity and thermal expansion coefficient, an imidazole compound may be used in combination with an organic peroxide or a carboxylate.
- organic peroxides ⁇ , ⁇ ′-bis(t-butylperoxy)diisopropylbenzene may be selected, and among carboxylates, manganese naphthenate may be selected.
- the content ratio of the component (E) is not specifically limited, but for example, the ratio may be 0.01 to 10 parts by mass relative to 100 parts by mass of the sum total of the components (A) and the component (B) in the present invention, or may be 0.01 to 5 parts by mass. Using the component (E) in the range tends to secure better heat resistance and storage stability.
- the component (F) includes phosphorus flame retardants, metal hydrates, halogen flame retardants, etc. From the viewpoint of environmental issues, phosphorus flame retardants and metal hydrates may be used. One alone or two or more kinds of flame retardants (F) may be used either singly or as combined.
- the phosphorus flame retardant for use herein is not specifically limited and may be any ordinary flame retardant containing a phosphorus atom, including inorganic phosphorus flame retardants and organic phosphorus flame retardants. From the viewpoint of environmental issues, those not containing a halogen atom may be selected. From the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy, organic phosphorus flame retardants may be used.
- inorganic phosphorus flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, etc.; inorganic nitrogen-containing phosphorus compounds such as phosphoric amide, etc.; phosphoric acid; phosphine oxide, etc.
- organic phosphorus flame retardants examples include aromatic phosphates, monosubstituted phosphonic diesters, disubstituted phosphinates, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, etc.
- aromatic phosphate compounds, and metal salts of disubstituted phosphinic acids may be selected.
- metal salts may be any of lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts, or may be aluminum salts.
- aromatic phosphates may be selected.
- aromatic phosphates examples include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 1,3-phenylenebis(di-2,6-xylenyl phosphate), bisphenol A bis(diphenyl phosphate), 1,3-phenylenebis(diphenyl phosphate), etc.
- Examples of the monosubstituted phosphonic diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate, etc.
- disubstituted phosphinates examples include phenyl diphenylphosphinate, methyl diphenylphosphinate, etc.
- Metal salts of disubstituted phosphinic acids include metal salts of dialkylphosphinic acids, metal salts of diallylphosphinic acids, metal salts of divinylphosphinic acids, metal salts of diarylphosphinic acids, etc. These metal salts may be any of lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts, and aluminum salts may be selected.
- organic nitrogen-containing phosphorus compounds examples include phosphazene compounds such as bis(2-allylphenoxy)phosphazene, dicresylphosphazene, etc.; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; melam polyphosphate, etc.
- the cyclic organic phosphorus compounds include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.
- At least one may be selected from aromatic phosphates, metal salts of disubstituted phosphinic acids and cyclic organic phosphorus compounds, or at least one may be selected from metal salts of disubstituted phosphinic acids and cyclic organic phosphorus compounds, or a metal salt of a disubstituted phosphinic acid and a cyclic organic phosphorus compound may be used in combination.
- the metal salt of a disubstituted phosphinic acid may be a metal salt of a dialkylphosphinic acid, or may be an aluminum salt of a dialkylphosphinic acid.
- the cyclic organic phosphorus compound may be 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phsophaphenanthrene-10-oxide.
- the blend ratio of the metal salt of a disubstituted phosphinic acid to the cyclic organic phosphorus compound may be 0.6 to 2.5 by mass, or may be 0.9 to 2, or may be 1 to 2, or may be 1.2 to 2.
- the aromatic phosphates may be aromatic phosphates represented by the following general formula (F-1) or (F-2), and the metal salts of a disubstituted phosphinic acid may be metal salts of a disubstituted phosphinic acid represented by the following general formula (F-3).
- R F1 to R F5 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom.
- e and f each independently represent an integer of 0 to 5
- g, h and i each independently represent an integer of 0 to 4.
- R F6 and R F7 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms.
- M represents a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom, or a zinc atom.
- m1 represents an integer of 1 to 4.
- the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R F1 to R F5 represent include the same ones as those of R 1 in the above-mentioned general formula (I).
- e and f each may be an integer of 0 to 2, or may be 2.
- g, h and i each may be an integer of 0 to 2, or may be 0 or 1, or may be 0.
- the aliphatic hydrocarbon group having 1 to 5 carbon atoms that R F6 and R F7 represent include the same ones as those of R 1 in the general formula (I).
- the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and may be an ethyl group.
- Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms that R F6 and R F7 represent include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, etc.
- the aromatic hydrocarbon group may be an aromatic hydrocarbon group having 6 to 10 carbon atoms.
- m1 represents a valence of a metal ion, that is, it varies within a range of 1 to 4 depending on the kind of M.
- M may be an aluminum atom.
- m1 is 3.
- metal hydrate examples include aluminum hydroxide hydrate, magnesium hydroxide hydrate, etc. One alone or two or more kinds of these may be used either singly or as combined.
- the metal hydroxide may correspond to an inorganic filler, but in the case of a material that imparts flame retardancy, this is grouped in a flame retardant.
- the halogen flame retardant includes a chlorine-based flame retardant, a bromine-based flame retardant, etc.
- the chlorine-based flame retardant include paraffin chloride, etc.
- the bromine-based flame retardant include brominated epoxy resins such as brominated bisphenol A-type epoxy resin, brominated phenol-novolak-type epoxy resin, etc.; brominated addition-type flame retardants such as hexabromobenzene, pentabromotoluene, ethylenebis(pentabromophenyl), ethylenebis-tetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, 2,4,6-tris(tribrom
- addition-type means that bromine has been introduced into the polymer in a form not chemically bonding thereto, that is, bromine has been blended in the polymer
- unsaturated double bond group-containing brominated reaction-type flame retardants such as tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A-type dimethacrylate, pentabromobenzyl acrylate, styrene bromide, etc.
- reaction-type means that bromine has been introduced into the polymer in a form chemically bonding thereto
- the content ratio of the phosphorus flame retardant in the resin composition of the present invention is not specifically limited, but for example, the phosphorus atom content in the resin composition in terms of the solid content therein (sum total of the other components than the component (D)) may be 0.2 to 5% by mass, or may be 0.3 to 3% by mass.
- the phosphorus atom content is 0.2% by mass or more, better flame retardancy tends to be attained.
- the phosphorus atom content is 5% by mass or less, better formability, high adhesion to conductor, excellent heat resistance and high glass transition temperature tend to be attained.
- the content thereof may be 20 parts by mass or less relative to 100 parts by mass of the sum total of the components (A) to (C), or may be 10 parts by mass or less, or may be 5 parts by mass or less.
- any other flame retardant than a phosphorus flame retardant and a halogen flame retardant is contained in the resin composition of the present invention
- the content thereof may be, though not specifically limited thereto, 0.5 to 20 parts by mass relative to 100 parts by mass of the sum total of the components (A) to (C), or may be 1 to 15 parts by mass, or may be 1 to 10 parts by mass, or may be 1 to 6 parts by mass.
- the resin composition of the present invention may contain a flame retardant promoter, for example, an inorganic flame retardant promoter such as antimony trioxide, zinc molybdate, etc.
- a flame retardant promoter for example, an inorganic flame retardant promoter such as antimony trioxide, zinc molybdate, etc.
- the content ratio thereof is not specifically limited, but may be, for example, 0.1 to 20 parts by mass relative to 100 parts by mass of the sum total of the component (A) and the component (B), or may be 0.1 to 10 parts by mass. Containing a flame retardant promoter in such a range, the resin composition tends to realize better chemical resistance.
- the resin composition of the present invention may adequately contain a resin material such as a known thermoplastic resin, an elastomer, etc., as well as a coupling agent, an antioxidant, a thermal stabilizer, an antistatic agent, a UV absorbent, a pigment, a colorant, a lubricant, etc.
- a resin material such as a known thermoplastic resin, an elastomer, etc.
- a coupling agent such as a known thermoplastic resin, an elastomer, etc.
- an antioxidant such as a known thermoplastic resin, an elastomer, etc.
- the resin composition of the present invention may contain an organic solvent, from the viewpoint of easy handleability through dilution and from the viewpoint of easy production of prepreg to be mentioned hereinunder.
- organic solvent examples include, though not specifically limited thereto, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc.; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ether solvents such as tetrahydrofuran, etc.; aromatic solvents such as toluene, xylene, mesitylene, etc.; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.; sulfur atom-containing solvents such as dimethylsulfoxide, etc.; ester solvents such as y-butyrolactone, etc.
- alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl
- alcohol solvents, ketone solvents or nitrogen atom-containing solvents may be used, or acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone may be used, or methyl ethyl ketone may be used.
- One alone or two or more kinds of organic solvents may be used either singly or as combined.
- the content of the organic solvent in the resin composition of the present invention is not specifically limited, and the solid concentration may be 30 to 90% by mass, or may be 40 to 80% by mass, or may be 40 to 70% by mass, or may be 40 to 60% by mass.
- the resin composition whose solid concentration falls within the range secures good handleability and penetrability into substrate, and betters the appearance of prepreg to be produced, and the solid concentration of resin in the prepreg to be mentioned below can be readily controlled, therefore facilitating production of a prepreg having a desired thickness.
- the above-mentioned components (A) to (C), and the other optional components to be combined, and optionally an organic solvent are mixed in a known method to produce the resin composition of the present invention.
- the components may be dissolved or dispersed with stirring.
- the conditions for the mixing order, the temperature, the time and others are not specifically limited, and may be defined in any desired manner.
- the glass transition temperature of the laminate formed with the resin composition of the present invention is not specifically limited, but from the viewpoint of good soldering heat resistance and through-hole interconnection reliability, as well as excellent workability in producing electronic parts and others, the temperature is preferably 200° C. or higher. There is no specific limitation in point of the upper limit of the glass transition temperature, and for example, the temperature may be 1,000° C. or lower, or may be 500° C. or lower, or may be 300° C. or lower, or may be 240° C. or lower.
- the thermal expansion coefficient (in Z direction, not higher than Tg) of the laminate formed with the resin composition of the present invention is not specifically limited, but from the viewpoint of preventing the laminate from warping, the coefficient is preferably 45 ppm/° C. or less, more preferably 40 ppm/° C. or less.
- the lower limit of the thermal expansion coefficient is, though not specifically limited thereto, generally 30 ppm/° C. or more, preferably 35 ppm/° C. or more.
- the glass transition temperature and the thermal expansion coefficient are values measured according to IPC Standards, as described in the section of Examples.
- the dielectric constant and the dielectric dissipation factor of the laminate formed with the resin composition of the present invention are not specifically limited. From the viewpoint of favorable use in a high frequency zone, the dielectric constant at 10 GHz is preferably smaller, and may be 3.85 or less, or may be 3.75 or less, or may be 3.65 or less.
- the lower limit of the dielectric constant is not specifically limited, and may be, for example, 0.5 or more, or may be 1 or more, or may be 3 or more, or may be 3.4 or more.
- the dielectric dissipation factor is preferably smaller, and may be 0.007 or less, or may be 0.006 or less, or may be 0.005 or less.
- the lower limit of the dielectric dissipation factor is not specifically limited and is preferably smaller, and may be, for example, 0.0001 or more, or may be 0.002 or more, or may be 0.004 or more.
- the dielectric constant and the dielectric dissipation factor are values according to JPCA-TM001 (Triplate-line resonator method) as described in the section of Examples.
- the present invention also provides a prepreg containing the resin composition of the present invention and a sheet-form fiber-reinforced substrate.
- the prepreg is formed using the resin composition of the present invention and a sheet-form fiber-reinforced substrate, and more specifically, the prepreg is formed by impregnating or coating a sheet-form fiber reinforced substrate with the resin composition of the present invention, and drying the substrate. More specifically, for example, the substrate is dried by heating in a drying oven generally at a temperature of 80 to 200° C. for 1 to 30 minutes to semi-cure the resin (into a B-stage), thereby producing the prepreg of the present invention.
- the amount of the resin composition to be used may be defined so that the resin composition-derived solid concentration in the dried prepreg could be 30 to 90% by mass.
- the solid content is controlled to fall within the range, the laminate to be obtained using the resultant prepreg can achieve excellent formability.
- the sheet-form fiber reinforced substrate for the prepreg a known substrate used in a laminate for various electrically insulating materials is used.
- the materials for the sheet-form reinforced substrate include inorganic fibers of E glass, D glass, S glass, Q glass or the like; organic fibers of polyimide, polyester, tetrafluoroethylene or the like; mixtures thereof, etc.
- These sheet-form reinforced substrate may have, for example, a form of woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, etc.
- the thickness of the sheet-form fiber reinforced substrate there is no particular limitation, and, for example, the substrate having a thickness of about 0.02 to 0.5 mm can be used.
- the substrate having a surface treated with a coupling agent or the like or having a mechanically opening treated substrate can be used from the viewpoint of impregnation performance with the resin composition, and from the viewpoint of heat resistance, moisture absorption resistance, and processability of the laminate formed with the substrate.
- a hot melt method or a solvent method to be mentioned below may be employed as the method of impregnating or coating the sheet-form reinforced substrate with the resin composition.
- an organic solvent is not contained in the resin composition, and the method is (1) a method of once applying the composition onto a releasable sheet, and laminating it on a sheet-form reinforced substrate, or (2) a method of directly applying the resin composition to a sheet-form reinforced substrate using a die coater.
- the solvent method is a method of adding an organic solvent to the resin composition, and immersing a sheet-form reinforced substrate in the resultant resin composition so that the sheet-form reinforced substrate could be impregnated with the resin composition, and thereafter drying it.
- the laminate of the present invention contains the prepreg of the present invention and a metal foil.
- the laminate of the present invention is formed using the prepreg of the present invention and a metal foil, and more specifically, the laminate is formed by arranging a metal foil on one surface or both surfaces of one prepreg, or by arranging a metal foil on one surface of both surfaces of a multilayer prepreg prepared by layering two or more prepregs of the present invention, and thereafter molding the resultant structure under heat and pressure.
- the metal for the metal foil may be any one usable for electrically insulating materials, but from the viewpoint of electroconductivity, the metal may be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements, or may be copper or aluminium, or may be copper.
- the condition for thermal pressure forming is not specifically limited.
- the temperature may be 100° C. to 300° C.
- the pressure may be 0.2 to 10.0 MPa
- the time may be 0.1 to 5 hours.
- a method of using a vacuum press or the like to keep a vacuum state for 0.5 to 5 hours may be employed.
- the multilayer printed wiring board of the present invention is formed using the prepreg or the laminate of the present invention.
- the multilayer printed wiring board of the present invention can be produced using the prepreg or the laminate of the present invention by performing circuit formation processing and bonding processing for forming a multilayer by perforating, metal plating, etching for a metal foil or the like according to a known method.
- the resin composition, the resin film, the prepreg, the metal-clad laminate and the multilayer printed wiring board of the present invention are favorably used in electronic devices working with high frequency signals of 1 GHz or more, and are especially favorably used in electronic devices working with high frequency signals of 10 GHz or more.
- t-butylperoxyisopropyl monocarbonate and manganese naphthenate were added to the resultant solution to perform a reaction at a solution temperature of 90° C. for 4 hours, and then cooled to 70° C. to give a polyphenylene ether compound (A′) having a primary amino group at the end of the molecule.
- a small portion of the resultant reaction solution was taken and subjected to GPC (polystyrene-equivalent measurement, eluent: tetrahydrofuran). As a result, it was found that the peak derived from p-aminophenol disappeared and the polyphenylene ether compound had a number average molecular weight of about 9,200.
- reaction solution was taken and dropwise added to a methanol/benzene mixed solvent (mass ratio in the mixed solvent: 1:1) to cause reprecipitation, and the resultant purified solid material was subjected to FT-IR measurement.
- FT-IR measurement confirmed that a peak derived from a primary amino group appeared at around 3,400 cm ⁇ 1 .
- the number average molecular weight was measured by gel permeation chromatography (GPC) in which standard polystyrenes were used for obtaining a molecular weight conversion calibration curve.
- the calibration curve was obtained using standard polystyrenes: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [trade name, manufactured by Tosoh Corp.]) and approximated to a cubic equation. Conditions for GPC are shown below.
- the result of the FT-IR measurement confirmed that the peak at around 3,500 cm ⁇ 1 derived from a primary amino group disappeared and a peak of a carbonyl group appeared at 1,700 to 1,730 cm ⁇ 1 . Further, the solid material was subjected to GPC measurement (under the same conditions as mentioned above). As a result, the number average molecular weight was found to be about 9,400.
- a polyphenylene ether derivative (A-2) was produced in the same manner as in Production Example A-1 except that, instead of 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane was used, and the individual components with the formulation shown in Table 1 were used.
- the polyphenylene ether derivative (A-2) had a number average molecular weight of about 9,400.
- a polyphenylene ether derivative (A-3) was produced in the same manner as in Production Example A-1 except that, instead of 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 1,6-bismaleimido-(2,2,4-trimethyl)hexane was used, and the individual components with the formulation shown in Table 1 were used.
- the polyphenylene ether derivative (A-3) had a number average molecular weight of about 9,500.
- a polyphenylene ether derivative (A-4) was produced in the same manner as in Production Example A-2 except that, instead of p-aminophenol, m-aminophenol was used.
- the polyphenylene ether derivative (A-4) had a number average molecular weight of about 9,400.
- a polyphenylene ether derivative (A-5) was produced in the same manner as in Production Example A-2 except that p-aminophenol and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane were used and the individual components with the formulation shown in Table 1 were used.
- the polyphenylene ether derivative (A-5) had a number average molecular weight of about 5,000.
- a polyphenylene ether derivative (A-6) in Production Example A-6 was produced in the same manner as in Production Example A-2 except that p-aminophenol and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane were used and the individual components with the formulation shown in Table 1 were used.
- the polyphenylene ether derivative (A-6) had a number average molecular weight of about 12,000.
- BMI-5100 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, trade name (manufactured by Daiwa Kasei Industry Co., Ltd.)
- BMI-4000 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, trade name (manufactured by Daiwa Kasei Industry Co., Ltd.)
- BMI-TMH 1,6-bismaleimido-(2,2,4-trimethyl)hexane, trade name (manufactured by Daiwa Kasei Industry Co., Ltd.)
- a polyaminobismaleimide compound (B-2) was produced in the same manner as in Production Example B-1 except that, instead of 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline was used in the amounts shown in Table 2.
- a polyaminobismaleimide compound (B-3) was produced in the same manner as in Production Example B-1 except that, instead of 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane and 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide and 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline were used in the amounts shown in Table 2.
- BMI-5100 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, trade name, (manufactured by Daiwa Kasei Industry Co., Ltd.)
- BMI-4000 2,2-bis(4(4-maleimidophenoxy)phenyl)propane, trade name, (manufactured by Daiwa Kasei Industry Co., Ltd.)
- BAPP 2,2-bis(4-(4-aminophenoxy)phenyl)propane, trade name (manufactured by Wakayama Seika Kogyo Co., Ltd.)
- Bisaniline-P 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline, trade name (manufactured by Mitsui Chemicals, Inc.)
- Bisaniline-M 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline, trade name (manufactured by Mitsui Chemicals, Inc.)
- BADCy Primaset (registered trademark) BADCy, 2,2-bis(4-cyanatophenyl)propane (manufactured by Lonza Group AG)
- the resin composition (excluding inorganic filler) generally has a density of 1.20 to 1.25 g/cm 3 , and the inorganic filler used has a density of 2.2 to 3.01 g/cm 3 . Therefore, when 80 parts by mass of the inorganic filler is incorporated, relative to 100 parts by mass of the resin composition (excluding inorganic filler), the amount of the inorganic filler incorporated is about 30 to 34% by volume.
- the resin composition obtained in each Example was applied to glass cloth having a thickness of 0.1 mm (E glass, manufactured by Nitto Boseki Co., Ltd.), and then dried by heating at 160° C. for 7 minutes to prepare a prepreg having a resin content of about 54% by mass.
- 6 sheets of the prepared prepreg were stacked on one another, and low profile copper foils having a thickness of 18 ⁇ m (FV-WS, M-side Rz: 1.5 ⁇ m; manufactured by The Furukawa Electric Co., Ltd.) were disposed respectively on the top and bottom of the resultant laminate so that the M-side of each copper foil was in contact with the laminate, and subjected to hot pressing under conditions such that the temperature was 230° C. (200° C. in Comparative Examples 5 and 6), the pressure was 3.9 MPa, and the time was 180 minutes to prepare a double-sided copper-clad laminate (thickness: 0.8 mm).
- the appearance of the above-obtained prepreg was examined. The appearance was visually examined, and the prepreg was evaluated according to the criteria shown below.
- the prepreg surface has some unevenness, streak, foaming, phase separation and the like, and lacks surface smoothness.
- the formability, the dielectric properties, the copper foil peel strength, the glass transition temperature, the thermal expansion coefficient, the soldering heat resistance, and the flame retardancy thereof were evaluated.
- the methods for evaluation of the properties of the copper-clad laminate are as described below.
- the appearance of the laminate having etched copper foils on both sides was examined to evaluate the formability.
- the formability was visually evaluated, and the laminate was evaluated according to the following criteria.
- the laminate has some unevenness, streak, thinned area, voids or the like, and lacks surface smoothness.
- the copper-clad laminate was immersed in a copper etchant, 10 mass % solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Corporation) to remove the copper foil, and a test piece of 2 mm ⁇ 85 mm was cut out of the resultant substrate for evaluation.
- test piece was tested according to JPCA-TM001 (Triplate-line resonator method) at 10 GHz band.
- Copper foil peel strength was measured in accordance with JIS-C-6481 (1996) to thereby determine the adhesion to conductor.
- a soldering heat resistance was evaluated using a 50 mm square test specimen having etched copper foils on both sides as follows. 3 specimens in a dry state and 3 specimens, which had been treated in a pressure cooker test (PCT) apparatus (conditions: 121° C., 2.2 atm.) for a predetermined period of time (1, 3, or 5 hours), were immersed in molten solder at 288° C. for 20 seconds, and then the appearance of each of the resultant specimens was visually examined.
- PCT pressure cooker test
- the figures shown in the tables mean, among the 3 specimens obtained after immersed in the solder, the number of the specimen or specimens in which a defect, such as the occurrence of blistering or measling, was not recognized in the laminate.
- thermomechanical analyzer (TMA) [manufactured by TA Instruments Japan Corporation, Q400 (Model Number)] to measure the glass transition temperature (Tg) and the thermal expansion coefficient (linear expansion coefficient, thickness direction, temperature range: 30 to 150° C.) thereof.
- the copper-clad laminate was immersed in a copper etchant, 10 mass % solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Corporation) to remove the copper foil, and a test piece having a length of 127 mm and a width of 12.7 mm was cut out of the resultant substrate for evaluation.
- the test piece was tested according to the test method (V method) of UL94 to evaluate the flame retardancy thereof.
- the lower edge of the test piece held vertically was exposed to 20-mm flame for 10 seconds, twice in every test.
- the evaluation was carried out according to the criteria in the V method of UL94.
- BMI-4000 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane (trade name, manufactured by Daiwa Kasei Industry Co., Ltd.)
- NC-3000H biphenylaralkyl-type epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd.)
- NC-7000L naphthol novolak-type epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd.)
- Tuftec (registered trademark) P2000: SBBS, styrene content 67% by mass (manufactured by Asahi Kasei Chemicals Corporation)
- Septon (registered trademark) 2005: SEPS, styrene content 20% by mass (manufactured by Kuraray Co., Ltd.)
- TOPAS registered trademark
- Perbutyl (registered trademark) P ⁇ , ⁇ ′-bis(t-butylperoxy)diisopropylbenzene (trade name, manufactured by NOF Corp.)
- G-8009L isocyanate-masked imidazole (addition product of hexamethylene-diisocyanate resin and 2-ethyl-4-methylimidazole) (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
- OP-935 aluminum dialkylphosphinate, metal salt of disubstituted phosphinic acid, phosphorus content: 23.5% by mass (trade name, manufactured by Clariant Corp.)
- HCA-HQ 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, cyclic organic phosphorus compound, phosphorus content: 9.6% by mass (manufactured by Sanko Co., Ltd.)
- Examples of the present invention are excellent in compatibility of the resin compositions and appearance of the prepregs, and the copper-clad laminates produced using these are good and well-balanced in all the formability, the high frequency properties (dielectric properties), the adhesion to conductor, the soldering heat resistance, the glass transition temperature, the thermal expansion coefficient and the flame retardancy.
- Comparative Examples 13 to 20 some resin compositions and prepregs are not good in compatibility and appearance (Comparative Examples 13 to 20).
- the copper-clad laminates of Comparative Examples are inferior to those of Examples in point of any of formability, dielectric properties, adhesion to conductor, soldering heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy.
- thermosetting resin composition along with a polyphenylene ether derivative having a specific structure and a styrenic thermoplastic elastomer, a resin composition having good compatibility, especially excellent high frequency properties (low dielectric constant, low dielectric dissipation factor), high adhesion to conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient and high flame retardancy can be obtained.
- the material cost and the production cost for substrate material can be suppressed, and the working environment is excellent, and therefore, the prepreg and the laminate to be provided using the resin composition can be favorably used for use for electronic parts such as multilayer printed wiring boards, etc.
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Abstract
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- wherein R1 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and x represents an integer of 0 to 4.
Description
- The present invention relates to a resin composition containing a polyphenylene ether derivative, and to a prepreg, a laminate and a multilayer printed wiring board.
- Signals used in mobile communication devices, such as a cell phone, base station apparatuses for them, network infrastructure devices, such as a server and a router, large-sized computers, and the like are being increased in the speed and capacity. In accordance with this, printed wiring boards mounted on these electronic devices are required to adapt to high-frequency signals, and a substrate material having excellent dielectric characteristics (low dielectric constant and low dielectric dissipation factor; hereinafter these may be referred to as high frequency properties) in a high frequency range that enable reduction of a transmission loss is demanded. Recently, as such applications that handle high-frequency signals, practical realization and practical use planning of novel systems that handle high-frequency wireless signals in an ITS field (in connection with automobiles and traffic systems) as well as in a field of indoor short-distance communications systems, in addition to the above-mentioned electronic devices, is being promoted, and in future, low transmission-loss substrate materials are expected to be required for the printed wiring boards to be mounted on these devices.
- Further, in view of the environmental problems encountered in recent years, mounting of electronic parts using a lead-free solder and achieving flame retardancy free of a halogen are demanded, and therefore the material for a printed wiring board is needed to have higher heat resistance and more excellent flame retardancy than conventional.
- Conventionally, for a printed wiring board required to have a low transmission loss, a polyphenylene ether (PPE) resin has been used as a heat-resistant thermoplastic polymer excellent in high frequency properties. For example, a method of using a polyphenylene ether and a thermosetting resin as combined has been proposed. Specifically, a resin composition containing a polyphenylene ether and an epoxy resin (see, for example, PTL 1), a resin composition using a polyphenylene ether in connection with a cyanate ester resin having a low dielectric constant among thermosetting resins (see, for example, PTL 2) and the like have been disclosed.
- However, the resin compositions described in the above-mentioned PTL's 1 and 2 are unsatisfactory collectively in the high frequency properties in a GHz region, the adhesion to conductor, the low thermal expansion coefficient, and the flame retardancy. In addition, the compatibility of polyphenylene ether with a thermosetting resin is low, and therefore the heat resistance of the resultant resin composition may often lower.
- Meanwhile, the present inventors have proposed a resin composition having a polyphenylene ether resin and a polybutadiene resin as a base, wherein the resin composition can be improved in the compatibility, heat resistance, low thermal expansion coefficient, adhesion to conductor, and the like by performing semi-IPN (semi-interpenetrating network) formation in the production stage (A-stage) of producing a resin composition containing an organic solvent (for example, PTL 3). However, the substrate material recently used for a printed wiring board is not only required to adapt to high-frequency signals, but also required to have high adhesion to conductor, low thermal expansion coefficient, high glass transition temperature, high flame retardancy, and the like due to the demands for an increase in the density, high reliability, and adaptability to consideration of the environment.
- For example, the adhesion to conductor is desired to be 0.6 kN/m or more, in terms of a copper foil peel strength as measured using a low profile copper foil (Rz: 1 to 2 μm) having a very small surface roughness on the side to be bonded to resin.
- Further, the substrate material for printed wiring board used in the application of network related devices, such as a server and a router, is needed to be stacked into the increased number of layers as the density of the wiring board is increased, and therefore the substrate material is required to have high reflow heat resistance and through-hole reliability. The glass transition temperature of the material as a yardstick for the above properties is desirably 200° C. or higher, and the thermal expansion coefficient (in the Z-direction at the Tg or lower) is desirably 45 ppm/° C. or less, further desirably 40 ppm/° C. or less. For achieving low thermal expansion property, the incorporation of an inorganic filler into the resin composition is effective; however, in a multilayer printed wiring board with the increased number of layers, for surely obtaining the flow properties of the resin for circuit packing, the amount of the inorganic filler to be incorporated is restricted. Therefore, it is desired that even when the amount of the inorganic filler incorporated is relatively small, the resultant resin composition is desired to secure the above-mentioned required values.
- With respect to high frequency properties, excellent dielectric properties in a higher frequency range are desired, and a substrate material using an ordinary E glass substrate is desired to have a dielectric constant of 3.8 or less, more desirably 3.7 or less, and even more desirably 3.6 or less, and to have an dielectric dissipation factor of 0.007 or less, more desirably 0.006 or less. Furthermore, a substrate material generally tends to have an increased dielectric dissipation factor at a higher frequency, but is increasingly strongly needed to satisfy the above-mentioned required values in a 10 GHz or more band which is a frequency band higher than the conventional 1 to 5 GHz band for the dielectric properties values.
- PTL 1: JP 58-069046 A
- PTL 2: JP 61-018937 B
- PTL 3: JP 2008-95061 A
- In consideration of the current situation as above, an object of the present invention is to provide a resin composition having especially excellent compatibility and having good dielectric properties in a high frequency range (low dielectric constant and low dielectric dissipation factor), high adhesion to conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient, and high flame retardancy, and to provide a prepreg, a laminate, and a multilayer printed wiring board using the resin composition.
- The present inventors have conducted extensive and intensive studies with a view toward solving the above-mentioned problems. As a result, the inventors have found that a prepreg and a laminate using a resin composition that contains a polyphenylene ether derivative having a specific molecular structure, a specific thermosetting resin and a styrenic thermoplastic elastomer can express excellent high frequency properties, high heat resistance, high adhesion to conductors, high glass transition temperature, low thermal expansion coefficient and high flame retardancy, and have completed the present invention.
- That is, the present invention relates to the following [1] to [16].
- [1] A resin composition containing:
- (A) a polyphenylene ether derivative having an N-substituted maleimide structure-containing group and a structural unit represented by the following general formula (I) in one molecule,
- (B) at least one thermosetting resin selected from the group consisting of an epoxy resin, a cyanate resin and a maleimide compound, and
- (C) a styrenic thermoplastic elastomer:
- wherein R1 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and x represents an integer of 0 to 4.
- [2] The resin composition according to the above [1], wherein the N-substituted maleimide structure-containing group is a group represented by the following general formula (Z):
- wherein R2 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, y represents an integer of 0 to 4, and A1 represents a group represented by the following general formula (II), (III), (IV) or (V):
- wherein R3 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, p represents an integer of 0 to 4:
- wherein R4 and R5 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a group represented by the following general formula (III-1), and q and r each independently represent an integer of 0 to 4:
- wherein R6 and R7 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A3 represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, and s and t each independently represent an integer of 0 to 4:
- wherein n represents an integer of 0 to 10:
- wherein R8 and R9 each independently represent a hydrogen atom, or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and u represents an integer of 1 to 8.
- [3] The resin composition according to the above [1] or [2], wherein the structural unit represented by the general formula (I) is a structural unit represented by the following formula (I′):
- [4] The resin composition according to the above [2] or [3], wherein A1 in the general formula (Z) is a group represented by any of the following formulae:
- [5] The resin composition according to any one of the above [1] to [4], wherein the number average molecular weight of the component (A) is from 5,000 to 12,000.
- [6] The resin composition according to any one of the above [1] to [5], wherein the maleimide compound as the component (B) is a polymaleimide compound (a) having at least two N-substituted maleimide groups in one molecule, or a polyaminobismaleimide compound (c) represented by the following general formula (VI):
- wherein A4 has the same definition as that of A1 in the general formula (Z), A5 represents a group represented by the following general formula (VII):
- wherein R17 and R18 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom, A8 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or a group represented by the following general formula (VII-1) or (VII-2), and q′ and r′ each independently represent an integer of 0 to 4:
- wherein R19 and R20 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A9 represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, and s′ and t′ each independently represent an integer of 0 to 4:
- wherein R21 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A10 and A11 each independently represent an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond, and w represents an integer of 0 to 4.
- [7] The resin composition according to any one of the above [1] to [6], wherein the content ratio of the component (A) to the component (B) [(A)/(B)] is from 5/95 to 80/20 by mass.
- [8] The resin composition according to any one of the above [1] to [7], wherein the component (C) is at least one selected from a styrene-butadiene-styrene block copolymer hydrogenate (SEBS, SBBS), a styrene-isoprene-styrene block copolymer hydrogenate (SEPS) and a styrene-maleic anhydride copolymer (SMA).
- [9] The resin composition according to any one of the above [1] to [8], wherein the content ratio of the component (C) is from 5 to 60 parts by mass relative to 100 parts by mass of the sum total of the components (A) to (C).
- [10] The resin composition according to any one of the above [1] to [9], further containing an inorganic filler (D).
- [11] The resin composition according to any one of the above [1] to [10], further containing a curing accelerator (E).
- [12] The resin composition according to any one of the above [1] to [11], further containing a flame retardant (F).
- [13] The resin composition according to any one of the above [1] to [12], further containing an organic solvent.
- [14] A prepreg including the resin composition of any one of the above [1] to [13] and a sheet-form fiber reinforced substrate.
- [15] A laminate including the prepreg of the above [14] and a metal foil.
- [16] A multilayer printed wiring board including the prepreg of the above [14] or the laminate of the above [15].
- The resin composition of the present invention has particularly good compatibility, excellent high frequency properties (low dielectric constant, low dielectric dissipation factor), high adhesion to conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient and high flame retardancy. Accordingly, the prepreg and the laminate to be obtained using the resin composition can be favorably used for electronic parts such as multilayer printed wiring boards, etc.
- Embodiments of the present invention are described in detail hereinunder.
- One aspect of the present invention is a resin composition containing:
- (A) a polyphenylene ether derivative having an N-substituted maleimide structure-containing group and a structural unit represented by the following general formula (I) in one molecule [hereinafter this may be simply abbreviated as polyphenylene ether derivative (A) or component (A)],
- (B) at least one thermosetting resin selected from the group consisting of an epoxy resin, a cyanate resin and a maleimide compound [hereinafter this may be simply abbreviated as thermosetting resin (B) or component (B)], and
- (C) a styrenic thermoplastic elastomer [hereinafter this may be abbreviated as component (C)].
- wherein R1 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, x represents an integer of 0 to 4.
- The components are described in order.
- The polyphenylene ether derivative (A) has an N-substituted maleimide structure-containing group and a structural unit represented by the above-mentioned general formula (I) in one molecule. In particular, since the polyphenylene ether derivative (A) has at least one N-substituted maleimide structure-containing group in one molecule, the resin composition can have excellent high frequency properties (low dielectric constant, low dielectric dissipation factor), high adhesion to conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient and high flame retardancy. Here, the thermal expansion coefficient as referred to in the present invention means a value also called a linear expansion coefficient.
- R1 in the general formula (I) each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and may be a methyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.
- Among the above, R1 may be an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
- x is an integer of 0 to 4, and may be an integer of 0 to 2, and may 2. When x is 1 or 2, R1 may be substituted at the ortho-position on the benzene ring (based on the substitution position of the oxygen atom). When x is 2 or more, plural R1's may be the same or different.
- Specifically, the structural unit represented by the general formula (I) may be a structural formula represented by the following general formula (I′).
- The N-substituted maleimide structure-containing group that the polyphenylene ether derivative (A) has may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy, a group containing a bismaleimide structure in which the nitrogen atoms of the two maleimide groups bond to each other via an organic group, and may be a group represented by the following general formula (Z).
- wherein R2 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, y represents an integer of 0 to 4, A1 represents a group represented by the following general formula (II), (III), (IV) or (V).
- The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R2 represents may be described in the same manner as that for the case of R1.
- y is an integer of 0 to 4, and may be an integer of 0 to 2, and may be 0. When y is an integer of 2 or more, plural R2's may be the same or different.
- The group represented by the general formula (II), (III), (IV) or (V) that A1 represents is as follows.
- wherein R3 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, p represents an integer of 0 to 4.
- The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R3 represents may be described in the same manner as that for the case of R1.
- p is an integer of 0 to 4, and, from the viewpoint of easy availability, may be an integer of 0 to 2, or 0 or 1, or 0. When p is an integer of 2 or more, plural R3's may be the same or different.
- wherein R4 and R5 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a group represented by the following general formula (III-1), q and r each independently represent an integer of 0 to 4.
- The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R4 and R5 represent include the same ones as those for R1. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and may be a methyl group or an ethyl group, and may be an ethyl group.
- Examples of the alkylene group having 1 to 5 carbon atoms that A2 represents include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc. The alkylene group may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy, an alkylene group having 1 to 3 carbon atoms, or may be a methylene group.
- Examples of the alkylidene group having 2 to 5 carbon atoms that A2 represents include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc. Among these, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy, it may be an isopropylidene group.
- Among the above-mentioned choices, A2 may be an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.
- q and r each are independently an integer of 0 to 4, and, from the viewpoint of easy availability, may be an integer of 0 to 2, or 0 or 2. When q or r is an integer of 2 or more, plural R4's or plural R5's each may be the same or different.
- The group represented by the general formula (III-1) that A2 represents is as follows.
- wherein R6 and R7 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A3 represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, s and t each independently represent an integer of 0 to 4.
- The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R6 and R7 represent may be described in the same manner as that for the case of R4 and R5.
- The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms that A3 represents include the same ones as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms that A2 represents.
- From among the above-mentioned choices, the alkylidene group having 2 to 5 carbon atoms may be selected for A3.
- s and t each are independently an integer of 0 to 4, and, from the viewpoint of easy availability, may be an integer of 0 to 2, or may be 0 or 1, or may be 0. When s or t is an integer of 2 or more, plural R6's or plural R7's each may be the same or different.
- wherein n represents an integer of 0 to 10.
- From the viewpoint of easy availability, n may be an integer of 0 to 5, or may be an integer of 0 to 3.
- wherein R8 and R9 each independently represent a hydrogen atom, or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, u represents an integer of 1 to 8.
- The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R8 and R9 represent may be described in the same manner as that for the case of R1.
- u is an integer of 1 to 8, and may be an integer of 1 to 3, or may be 1.
- A1 in the group represented by the general formula (Z) may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy, a group represented by any of the following formulae.
- The polyphenylene ether derivative (A) may be a polyphenylene ether derivative represented by the following general formula (A′).
- wherein A1, R1, R2, x and y are as defined hereinabove, m represents an integer of 1 or more.
- m may be an integer of 1 to 300, or may be an integer of 10 to 300, or may be an integer of 30 to 200, or may be an integer of 50 to 150.
- The polyphenylene ether derivative (A) may be a polyphenylene ether derivative represented by any of the following formulae.
- wherein m is the same as m in the general formula (A′).
- From the viewpoint of inexpensive raw materials, the derivative may be a polyphenylene ether derivative of the above formula (A′-1), from the viewpoint of excellent dielectric properties and low water absorbability, it may be a polyphenylene ether derivative represented by the formula (A′-2), and from the viewpoint of excellent adhesion to conductor and mechanical properties (elongation, strength at break, etc.), it may be a polyphenylene ether derivative represented by the formula (A′-3). Accordingly, in conformity to the intended properties, one alone or two or more of the polyphenylene ether derivatives of the formulae (A′-1) to (A′-3) may be used either singly or as combined.
- The number average molecular weight of the polyphenylene ether derivative (A) of the present invention may be 5,000 to 12,000, or may be 7,000 to 12,000, or may be 7,000 to 10,000. When the number average molecular weight is 5,000 or more, the resin composition of the present invention and the prepreg and the laminate using the composition tend to have a more favorable glass transition temperature. When the number average molecular weight is 12,000 or less, the resin composition of the present invention tend to be readily molded into a laminate with better formability.
- In this description, the number average molecular weight is a value calculated based on the calibration curve drawn using a standard polystyrene, according to gel permeation chromatography (GPC), and more precisely, a value measured according to the number average molecular weight measurement method described in the section of Examples.
- The polyphenylene ether derivative (A) may be obtained, for example, according to the production method mentioned below.
- First, an aminophenol compound represented by the following general formula (VIII) [hereinafter referred to as aminophenol compound (VIII)] is reacted with a polyphenylene ether having, for example, a number average molecular weight of 15,000 to 25,000 in an organic solvent in a mode of known redistribution reaction, as associated with reduction in the polyphenylene ether, to thereby produce a polyphenylene ether compound having a primary amino group in one molecule (A″) (hereinafter this may be simply referred to as polyphenylene ether compound (A″)), and then the polyphenylene ether compound (A″) is reacted with a bismaleimide compound represented by the general formula (IX) [hereinafter referred to as bismaleimide compound (IX)] in a mode of Michael addition reaction to produce the polyphenylene ether derivative (A).
- wherein R2 and y are the same as those in the general formula (I).
- wherein A1 is the same as in the general formula (I).
- Examples of the aminophenol compound (VIII) include o-aminophenol, m-aminophenol, p-aminophenol, etc. Among these, from the viewpoint of the reaction yield in producing the polyphenylene ether compound (A″), as well as the heat resistance in producing resin composition, prepreg and laminate, the compound may be m-aminophenol or p-aminophenol, or may be p-aminophenol.
- The molecular weight of the polyphenylene ether compound (A″) may be controlled by the amount to be used of the aminophenol compound (VIII), and when the amount of the aminophenol compound (VIII) used is larger, the molecular weight of the polyphenylene ether compound (A″) is lower. Namely, the amount to be used of the aminophenol compound (VIII) may be adequately controlled so that the number average molecular weight of the polyphenylene ether derivative (A) to be produced finally could fall within a preferred range.
- The amount to be incorporated of the aminophenol compound (VIII) is not specifically limited, but for example, when the number average molecular weight of the polyphenylene ether to be reacted with the aminophenol compound (VIII) is 15,000 to 25,000, the amount may fall within a range of 0.5 to 6 parts by mass relative to 100 parts by mass of the polyphenylene ether to give a polyphenylene ether derivative (A) having a number average molecular weight of 5,000 to 12,000.
- Examples of the organic solvent for use in the production step for the polyphenylene ether compound (A″) include, though not specifically limited thereto, alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; aromatic hydrocarbons such as toluene, xylene, mesitylene, etc.; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate, etc.; nitrogen-containing compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. One alone or two or more kinds of these may be used either singly or as combined. Among these, from the viewpoint of solubility, toluene, xylene and mesitylene may be selected.
- In the production step for the polyphenylene ether compound (A″), a reaction catalyst may be used as needed. To the reaction catalyst, for example, the reaction catalyst in redistribution reaction is applicable. For example, from the viewpoint of producing the polyphenylene ether compound (A″) having a stable number average molecular weight with good reproducibility, an organic peroxide such as t-butylperoxyisopropyl monocarbonate or the like and a metal carboxylate such as manganese naphthenate or the like may be used as combined. The amount of the reaction catalyst to be used is not specifically limited. From the viewpoint of the reaction speed and antigelation in producing the polyphenylene ether compound (A″), for example, the amount of the organic peroxide may be 0.5 to 5 parts by mass and that of the metal carboxylate may be 0.05 to 0.5 parts by mass relative to 100 parts by mass of the polyphenylene ether to be reacted with the aminophenol compound (VIII).
- The aminophenol compound (VIII), the polyphenylene ether having a number average molecular weight of 15,000 to 25,000, an organic solvent and optionally a reaction catalyst are put in a reactor each in a predetermined amount, and reacted with heating, keeping the heat and stirring to give the polyphenylene ether compound (A″). For the reaction temperature and the reaction time in this step, the reaction conditions in known redistribution reaction are applicable.
- From the viewpoint of operability and antigelation, and from the viewpoint of controlling the molecular weight of the polyphenylene ether compound (A″) for obtaining the component (A) having a desired number average molecular weight, for example, the reaction may be carried out at a reaction temperature of 70 to 110° C. and for a reaction time of 1 to 8 hours.
- A solution of the polyphenylene ether compound (A″) thus produced in the manner as above may be continuously and directly fed to the next step of producing the polyphenylene ether derivative (A). In this stage, the solution of the polyphenylene ether compound (A″) may be cooled, or may be controlled to be at the reaction temperature in the next step. As needed, the solution may be concentrated to remove a part of the organic solvent, or may be diluted by adding an organic solvent thereto, as described below.
- Examples of the bismaleimide compound (IX) to be used in producing the polyphenylene ether derivative (A) include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(4-maleimidophenyl) sulfone, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) ketone, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(4-(4-maleimidophenoxy)phenyl) sulfone, 4,4′-bis(3-maleimidophenoxy)biphenyl, and 1,6-bismaleimido-(2,2,4-trimethyl)hexane. These may be used individually or in combination.
- Of these, bis(4-maleimidophenyl)methane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane may be selected.
- Bis(4-maleimidophenyl)methane may be used because the polyphenylene ether derivative containing the formula (A′-1) above is obtained and it is inexpensive. 3,3′-Dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide may be used because the polyphenylene ether derivative containing the formula (A′-2) above is obtained and exhibits excellent dielectric properties and low water absorption properties. 2,2-Bis(4-(4-maleimidophenoxy)phenyl)propane may be used because the polyphenylene ether derivative containing the formula (A′-3) above is obtained and exhibits high adhesion to conductor and excellent mechanical properties (elongation, strength at break).
- The amount of the bismaleimide compound (IX) is determined according to the amount of the aminophenol compound (VIII) used. Specifically, the bismaleimide compound may be incorporated so that the equivalent ratio (Tb1/Ta1) of the maleimide group equivalent (Tb1) of the bismaleimide compound (IX) to the —NH2 group equivalent (Ta1) of the aminophenol compound (VIII) could be in the range of 2 to 6, or in a rage of 2 to 4. When the bismaleimide compound is used in the equivalent ratio range as above, the resin composition, the prepreg and the laminate of the present invention tend to have more excellent heat resistance, high glass transition temperature and high flame retardancy.
- In the Michael addition reaction conducted when producing the polyphenylene ether derivative (A), a reaction catalyst may be used as needed. With respect to the reaction catalyst used, there is no particular limitation. However, examples of the reaction catalyst include acidic catalysts, such as p-toluenesulfonic acid; amines, such as triethylamine, pyridine, and tributylamine; imidazole compounds, such as methylimidazole and phenylimidazole; and phosphorus catalysts, such as triphenylphosphine. These may be used individually or in combination. With respect to the amount of the reaction catalyst incorporated, there is no particular limitation. However, for example, relative to 100 parts by mass of the polyphenylene ether compound (A″), the reaction catalyst can be used in an amount in the range of 0.01 to 5 parts by mass.
- The bismaleimide compound (IX) and optionally a reaction catalyst and others are put into the solution of the polyphenylene ether compound (A″) solution each in a predetermined amount, and reacted with heating, keeping the heat and stirring in a mode of Michael reaction to give the polyphenylene ether derivative (A). Regarding the reaction conditions in this step, for example, from the viewpoint of operability and antigelation, the reaction temperature may be 50 to 160° C., and the reaction time may be 1 to 10 hours. In addition, in this step, an organic solvent may be added, or the reaction system may be concentrated as mentioned above, to thereby control the reaction concentration (solid concentration, and the solution viscosity. For the additional organic solvent, the organic solvents exemplified in the section of the production step for the polyphenylene ether compound (A″) are applicable, and one alone or two or more kinds of these may be used either singly or as combined. Among these, from the viewpoint of solubility, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N,N-dimethylformamide and N,N-dimethylacetamide may be selected.
- The reaction concentration (solid concentration) in the production step for the polyphenylene ether derivative (A) and the polyphenylene ether (A″) is not specifically limited, but, for example, in each production step, the concentration may be 10 to 60% by mass, and may be 20 to 50% by mass. When the reaction concentration is 10% by mass or more, the reaction speed is not too low, and tends to be favorable from the viewpoint of production cost. When the reaction concentration is 60% by mass or less, better solubility tends to be attained. If so, in addition, the solution viscosity may be low and the stirring efficiency tends to be good to suppress gelation.
- After production of the polyphenylene ether derivative (A), a part or all of the organic solvent may be optionally removed from the solution for concentration, or an additional organic solvent may be added thereto for dilution, in accordance with the operability in taking out the derivative from the reactor or with the use condition (for example, solution viscosity or solution concentration suitable for production of prepreg) in preparing the resin composition of the present invention by adding various thermosetting resins to the polyphenylene ether derivative (A). The additional organic solvent is not specifically limited, and one or more organic solvents mentioned above may be used.
- The formation of the polyphenylene ether compound (A″) and the polyphenylene ether derivative (A) in the above-mentioned production steps may be confirmed through GPC and IR analysis by sampling a small amount of the product after each step.
- First, with respect to the polyphenylene ether compound (A″), the production of a desired polyphenylene ether compound (A″) can be confirmed by GPC showing that the molecular weight is reduced to be lower than the polyphenylene ether having a number average molecular weight of 15,000 to 25,000 and that the peak of the aminophenol compound (VIII) as a raw material has disappeared, and by IR analysis showing that a peak of the primary amino group appears at 3,300 to 3,500 cm−1. With respect to the polyphenylene ether derivative (A) which has been purified by reprecipitation, the production of a desired polyphenylene ether derivative (A) can be confirmed by IR analysis showing that the peak of the primary amino group at 3,300 to 3,500 cm−1 has disappeared and that a peak of the carbonyl group of maleimide appears at 1,700 to 1,730 cm−1.
- The resin composition of the present invention tends to be more excellent in adhesion to conductor, heat resistance, thermal expansion coefficient, flame retardancy and workability (in drilling, cutting) than the resin composition containing the polyphenylene ether compound (A″) and the component (B) to be mentioned below.
- The resin component (B) contained in the resin composition of the present invention is at least one thermosetting resin selected from the group consisting of an epoxy resin, a cyanate resin and a maleimide compound. The maleimide compound does not include the above-mentioned polyphenylene ether derivative (A).
- The component (B) may be at least one thermosetting resin selected from the group consisting of an epoxy resins and a maleimide compound.
- The epoxy resin may be an epoxy resin having two or more epoxy groups in one molecule. Here, the epoxy resin is grouped into a glycidyl ether-type epoxy resin, a glycidylamine-type epoxy resin, a glycidyl ester-type epoxy resin, etc. Among these, a glycidyl ether-type epoxy resin may be selected.
- The epoxy resin is grouped into various types of epoxy resins depending on the difference in the main skeleton, and various types of the epoxy resins mentioned above may be further grouped into a bisphenol-type epoxy resin such as a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, etc.; an alicyclic epoxy resin; an aliphatic linear epoxy resin; a novolak-type epoxy resin such as a phenol-novolak-type epoxy resin, a cresol-novolak-type epoxy resin, a bisphenol A-novolak-type epoxy resin, a bisphenol F-novolak-type epoxy resin, etc.; a phenol-aralkyl-type epoxy resin, a stilbene-type epoxy resin, a dicyclopentadiene-type epoxy resin, a naphthalene skeleton-containing epoxy resin such as a naphthol-novolak-type epoxy resin, a naphthol-aralkyl-type epoxy resin, etc.; a biphenyl-type epoxy resin, a biphenylaralkyl-type epoxy resin; a xylylene-type epoxy resin; a dihydroanthracene-type epoxy resin; a dicyclopentadiene-type epoxy resin, etc.
- One alone or two or more kinds of epoxy resins may be used either singly or as combined. Among these, from the viewpoint of high frequency properties, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy, a naphthalene skeleton-containing epoxy resin and a biphenylaralkyl-type epoxy resin may be used.
- In the case where an epoxy resin is used as the component (B), if desired, a curing agent or a curing aid for epoxy resin may be used as combined. Examples of these include, though not specifically limited thereto, polyamine compounds such as diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, m-phenylenediamine, dicyandiamide, etc.; polyphenol compounds such as bisphenol A, phenol-novolak resin, cresol-novolak resin, bisphenol A-novolak resin, phenolaralkyl resin, etc.; acid anhydrides such as phthalic anhydride, pyromellitic anhydride, etc.; carboxylic acid compounds; active ester compounds, etc. One alone or two or more of these may be used either singly or as combined. The amount thereof to be used is not specifically limited and may be adequately controlled depending on the object. Among these, from the viewpoint of heat resistance, glass transition temperature, thermal expansion coefficient, storage stability and insulation reliability, polyphenol compounds and active ester compounds may be used.
- Examples of the cyanate resin include, though not specifically limited thereto, 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)ethane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, α,α′-bis(4-cyanatophenyl)-m-diisopropylbenzene, cyanate ester compound of phenol-added dicyclopentadiene polymer, phenol-novolak-type cyanate ester compound and cresol-novolak-type cyanate ester compound. One alone or two or more kinds of cyanate resins may be used either singly or as combined. Among these, from the viewpoint of production cost as well as from the viewpoint of total balance of high frequency properties and other properties, 2,2-bis(4-cyanatophenyl)propane may be used.
- In the case where a cyanate resin is used as the component (B), if desired, a curing agent or a curing aid for cyanate resin may be used as combined. Examples of these include, though not specifically limited thereto, monophenol compounds, polyphenol compounds, amine compounds, alcohol compounds, acid anhydrides, carboxylic acid compounds, etc. One alone or two or more of these may be used either singly or as combined. The amount of the curing agent and the curing aid to be used is not specifically limited and may be adequately controlled depending on the object. Among these, from the viewpoint of high frequency properties, heat resistance, moisture absorption resistance and storage stability, monophenol compounds may be used.
- In the case where a cyanate resin is used as combined with a monophenol compound, from the viewpoint of solubility in organic solvent, a method of pre-reacting them to give a phenol-modified cyanate prepolymer may be employed. Regarding the monophenol compound to be used in combination, all the prescribed amount thereof may be incorporated in prepolymerization, or the prescribed amount may be divided in portions and added portionwise before and after prepolymerization, but from the viewpoint of storage stability, the method of portionwise incorporating the compound may be employed.
- The maleimide compound is not specifically limited, but, for example, at least one of (a) a polymaleimide compound having at least two N-substituted maleimide groups in one molecule [hereinafter this may be referred to as component (a)] and (c) a polyaminobismaleimide compound represented by the following general formula (VI) [hereinafter this may be referred to as component (c)] may be contained. From the viewpoint of solubility in organic solvent, high frequency properties, adhesion to conductor and prepreg formability, the maleimide compound may be the polyaminobismaleimide compound (c).
- The polyaminobismaleimide compound (c) may be obtained, for example, by reacting the component (a) and an aromatic diamine compound (b) having two primary amino groups in one molecule [hereinafter this may be referred to as component (b)] in a mode of Michael addition reaction in an organic solvent:
- wherein A4 has the same definition as A1 in the above general formula (Z), and A5 is a group represented by the following general formula (VII):
- wherein R17 and R18 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom, A8 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or a group represented by the following general formula (VII-1) or (VII-2), and q′ and r′ each independently represent an integer of 0 to 4:
- wherein R19 and R20 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A9 represents an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, and s′ and t′ each independently represent an integer of 0 to 4:
- wherein R21 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A10 and A11 each independently represent an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, and w represents an integer of 0 to 4.
- The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that R17, R18, R19, R20 and R21 in the above general formula (VII), (VII-1) or (VII-2) represent include the same ones as those of R1 in the general formula (I). The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and may be a methyl group or an ethyl group.
- A4 in the general formula (VI) have the same definition as A1 in the general formula (Z).
- The alkylene group having 1 to 5 carbon atoms that A8 and A9 in the above general formula (VII), (VII-1) or (VII-2) represent, and the alkylidene group having 2 to 5 carbon atoms that A8 represents may be described in the same manner as that for the case of A2 in the general formula (III). The alkylene group having 1 to 5 carbon atoms that A10 and A11 in the general formula (VII-2) represent may be described in the same manner as that for the case of A2 in the general formula (III).
- q′ and r′ each are an integer of 0 to 4, and from the viewpoint of easy availability, both may be an integer of 0 to 2, or may be 0 or 2. s′ and t′ each are an integer of 0 to 4, and from the viewpoint of easy availability, both may be an integer of 0 to 2, or may be 0 or 1, or may be 0. w is an integer of 0 to 4, and from the viewpoint of easy availability, may be an integer of 0 to 2, or may be 0.
- The component (a) is not specifically limited, but for example, the same ones as those of the above-mentioned bismaleimide compound (IX) are applicable. Examples of the component (a) include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(4-maleimidophenyl) sulfone, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) ketone, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(4-(4-maleimidophenoxy)phenyl) sulfone, 4,4′-bis(3-maleimidophenoxy)biphenyl, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, etc. These may be used individually or in combination, depending on the object and use. The component (a) may be a bismaleimide compound, and may be bis(4-maleimidophenyl)methane from the viewpoint of inexpensiveness, may be 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide from the viewpoint of excellent dielectric properties and low water absorption, and may be 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane from the viewpoint of high adhesion to conductor and excellent mechanical properties (elongation, strength at break).
- As described above, the polyaminobismaleimide compound (c) may be obtained by reacting the above component (a) and an aromatic diamine compound (b) having two primary amino groups in one molecule in an organic solvent in a mode of Michael addition reaction.
- Examples of the component (b) include, though not specifically limited thereto, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ketone, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy)biphenyl, 1,3-bis(1-4-(4-aminophenoxy)phenyl)-1-methylethylkenzene, 1,4-bis(1-4-(4-aminophenoxy)phenyl)-1-methylethylkenzene, 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 3,3′-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis(4-(4-aminophenoxy)phenyl) sulfone, bis(4-(3-aminophenoxy)phenyl) sulfone, 9,9-bis(4-aminophenyl)fluorene, etc. These components (b) may be used individually or in combination.
- Among these, from the viewpoint of achieving high solubility in an organic solvent and high reaction rate for the synthesis as well as high heat resistance, the component may be selected from 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline, and 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline. From the viewpoint of the inexpensiveness in addition to the above-mentioned high solubility, high reaction rate, and high heat resistance, the component may be 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, or 4,4′-diamino-3,3′-diethyl-diphenylmethane. Further, from the viewpoint of achieving high adhesion to conductor in addition to the above-mentioned high solubility, high reaction rate, and high heat resistance, the compound may be 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline, or 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline. Furthermore, from the viewpoint of achieving excellent high-frequency properties and moisture absorption resistance in addition to the above-mentioned high solubility, high reaction rate, high heat resistance, and high adhesion to conductor, the component may be selected from 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline and 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline. According to the object and use, these may be used individually or in combination.
- With respect to the organic solvent used in producing the polyaminobismaleimide compound (c), there is no particular limitation. However, for example, the organic solvents mentioned above as examples in connection with the production step for the polyphenylene ether compound (A″) can be applied. These may be used individually or in combination. Of these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N,N-dimethylformamide, and N,N-dimethylacetamide may be used from the viewpoint of solubility.
- With respect to the amounts of the component (a) and the component (b) used in producing the component (c), the component (a) and the component (b) may be incorporated so that the equivalent ratio (Tb2/Ta2) of the maleimide group equivalent (Tb2) of the component (a) to the —NH2 group equivalent (Ta2) of the component (b) could be in the range of 1 to 10, or could be in the range of 2 to 10. When the component (a) and component (b) are used so that the equivalent ratio could be in the above range, the resin composition, the prepreg and the laminate of the present invention can have excellent high frequency properties, high adhesion to conductor, excellent heat resistance, high glass transition temperature and powerful flame retardancy.
- A reaction catalyst may not be used for the Michael addition reaction in producing the polyaminobismaleimide compound (c), but may be used as needed. The reaction catalyst is not specifically limited, and the reaction catalyst usable in the Michael addition reaction in producing the above-mentioned polyphenylene ether derivative (A) is applicable. Also as described above, the amount of the reaction catalyst to be incorporated is not specifically limited.
- In the case where a maleimide compound is used as the component (B), a curing agent for the maleimide compound, a crosslinking agent, a curing aid and other may be used. These are not specifically limited, and examples thereof include vinyl compounds such as styrene monomer, divinylbenzene, divinylbiphenyl, etc.; (meth)acrylate compounds; allyl compounds such as triallyl cyanurate, triallyl isocyanurate, etc.; polyamine compounds such as diaminodiphenylmethane, etc. One alone or two or more of these may be used either singly or as combined. The amount of these to be used is not also specifically limited, and may be adequately controlled depending on the object. Among these, from the viewpoint of high frequency properties and heat resistance, vinyl compounds or polyamine compounds may be used.
- The above-mentioned component (a) and component (b) and an organic solvent and optionally a reaction catalyst and others are put into a reactor each in a predetermined amount, and with heating, keeping the heat and stirring, these are reacted in a mode of Michael addition reaction to give the polyaminobismaleimide compound (c). For the reaction conditions in this step, for example, the reaction conditions in the Michael addition reaction in producing the above-mentioned polyphenylene ether derivative (A) are applicable.
- The reaction concentration (solid concentration) is not specifically limited, but may be 10 to 90% by mass, and may be 20 to 80% by mass. When the reaction concentration is 10% by mass or more, the reaction speed is not too low, and tends to be advantageous from the viewpoint of production cost. When the reaction concentration is 90% by mass or less, better solubility tends to be attained. If so, in addition, the solution viscosity may be low and the stirring efficiency tends to be good to suppress gelation. After production of the polyaminobismaleimide compound (c), a part or all of the organic solvent may be removed (for concentration), or an additional organic solvent may be added for dilution in accordance with the intended object, like in producing the polyphenylene ether derivative (A).
- The content of the component (A) is not specifically limited, but is, from the viewpoint of high frequency properties, preferably 3% by mass or more relative to 100 parts by mass of the sum total of the components (A) to (C), more preferably 5% by mass or more.
- The content of the component (B) is not specifically limited, but is, from the viewpoint of high frequency properties and formability, preferably 10 to 90% by mass relative to 100 parts by mass of the sum total of the components (A) to (C), more preferably 20 to 80% by mass.
- The content ratio of the component (A) to the component (B [(A)/(B)] is not specifically limited, and may be 5/95 to 80/20 by mass, may be 5/95 to 75/25, may be 5/95 to 70/30, and may be 10/90 to 70/30. When the content ratio of the component (A) to the total content of the component (A) and the component (B) is 5% by mass or more, more excellent high frequency properties and low moisture absorption tend to be attained. When the ratio is 80% by mass or less, more excellent heat resistance, more excellent formability and more excellent workability tend to be attained.
- The component (C) contained in the resin composition of the present invention is a styrenic thermoplastic elastomer. Containing the component (C), the resin composition of the present invention has good and well-balanced formability, high frequency properties (dielectric properties), adhesion to conductor, soldering heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy.
- Not specifically limited, the styrenic thermoplastic elastomer (C) may be any thermoplastic elastomer having a structural unit (see below) derived from a styrenic compound represented by the following general formula, and may be a thermoplastic elastomer having a styrene-derived structural unit (Ra=hydrogen atom, k=0).
- In the formula, Ra represents a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, Rb represents an alkyl group having 1 to 5 carbon atoms, k represents an integer of 0 to 5.
- Examples of the alkyl group having 1 to 5 carbon atoms that Ra and Rb represent include a methyl group, an ethyl group, an n-propyl group, etc., and the group may be an alkyl group having 1 to 3 carbon atoms, or may be a methyl group.
- Ra may be a hydrogen atom.
- k may be an integer of 0 to 2, or may be 0 or 1, or may be 0.
- The other structural unit than the styrenic compound-derived structural unit that the styrenic thermoplastic elastomer (C) has includes a butadiene-derived structural unit, an isoprene-derived structural unit, a maleic acid-derived structural unit, a maleic anhydride-derived structural unit, etc. One alone or two more kinds of styrenic thermoplastic elastomers (C) may be used either singly or as combined.
- The butadiene-derived structural unit and the isoprene-derived structural unit may be hydrogenated. In the case of hydrogenation, the butadiene-derived structural unit is a structural unit of a mixture of an ethylene unit and a butylene unit, and the isoprene-derived structural unit is a structural unit of a mixture of an ethylene unit and a propylene unit.
- From the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature and thermal expansion coefficient, the styrenic thermoplastic elastomer (C) may be at least one selected from a styrene-butadiene-styrene block copolymer hydrogenate (SEBS, SBBS), a styrene-isoprene-styrene block copolymer hydrogenate (SEPS) and a styrene-maleic anhydride copolymer (SMA).
- The styrene -butadiene-styrene block copolymer hydrogenate includes SEBS where the hydrogenation ratio of the carbon-carbon double bonds is generally 90% or more (or may be 95% or more), and SBBS where the carbon-carbon double bond at the 1,2-bond site in the butadiene block (see the left side of the following) has been partially hydrogenated (the hydrogenation ratio to all carbon-carbon double bonds is about 60 to 85%).
- In SEBS, the content of the styrene-derived structural unit (hereinafter this may be abbreviated as styrene content) may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature and thermal expansion coefficient, 5 to 80% by mass, or may be 5 to 70% by mass, or may be 10 to 70% by mass, or may be 10 to 50% by mass. The melt flow rate (MFR) of SEBS may be, though not specifically limited thereto, 0.1 to 20 g/10 min under the measurement condition at 230° C. and a load of 2.16 kgf (21.2 N), or may be 0.5 to 15 g/10 min.
- Examples of commercial products of SEBS include Tuftec (registered trademark) H Series and M Series manufactured by Asahi Kasei Chemicals Corporation, Septon (registered trademark) Series manufactured by Kuraray Co., Ltd., Crayton (registered trademark) G Polymer Series manufactured by Crayton Polymer Japan Corporation, etc.
- The styrene content in SBBS maybe, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature and thermal expansion, 40 to 80% by mass, or may be 50 to 75% by mass, or may be 55 to 75% by mass. The melt flow rate (MFR) of SBBS may be, though not specifically limited thereto, 0.1 to 10 g/10 min under the measurement condition at 190° C. and a load of 2.16 kgf (21.2 N), or maybe 0.5 to 10 g/10 min, or may be 1 to 6 g/10 min.
- Examples of commercial products of SBBS include Tuftec (registered trademark) P Series manufactured by Asahi Kasei Chemicals Corporation, etc.
- The hydrogenation ratio of the styrene-isoprene-styrene block copolymer hydrogenate (SEPS) may be 90% or more, or may be 95% or more. In SEPS, the styrene content may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature and thermal expansion, 5 to 60% by mass, or may be 5 to 50% by mass, or may be 10 to 40% by mass. The melt flow rate (MFR) of SEPS maybe, though not specifically limited thereto, 0.1 to 130 g/10 min under the measurement condition at 230° C. and a load of 2.16 kgf (21.2 N), or may be 10 to 100 g/10 min, or may be 50 to 90 g/10 min.
- Examples of commercial products of SEPS include Septon (registered trademark) Series manufactured by Kuraray Co., Ltd., Crayton G Polymer Series manufactured by Crayton Polymer Japan Corporation, etc.
- In the styrene-maleic anhydride copolymer (SMA), the styrene content may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature and thermal expansion coefficient, 20 to 90% by mass, or may be 40 to 90% by mass, or may be 50 to 90% by mass, or may be 55 to 85% by mass.
- In the styrene-maleic anhydride copolymer (SMA), the maleic anhydride-derived structural unit may be esterified.
- Examples of commercial products of SMA include SMA (registered trademark) Resin manufactured by Cray Valley Technology USA, etc.
- For all the styrenic thermoplastic elastomers (C), commercial products may be used. The styrene content and the melt flow rate (MFR) mentioned above are the values described in the manufacturer's catalogue or homepages.
- The content ratio of the component (C) may be, from the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature and thermal expansion coefficient, 5 to 60 parts by mass relative to 100 parts by mass of the sum total of the components (A) to (C), or may be 10 to 60 parts by mass, or may be 15 to 60 parts by mass, or may be 15 to 50 parts by mass, or may be 15 to 40 parts by mass. When the content ratio of the component (C) is 5 parts by mass or more relative to 100 parts by mass of the sum total of the components (A) to (C), high frequency properties and moisture absorption resistance tend to be better, and when 60 parts by mass or less, heat resistance, formability, workability and flame retardancy tend to be better.
- The resin composition of the present invention, if necessary, may contain at least one component selected from an inorganic filler (D) [hereinafter, frequently referred to as “component (D)”], a curing accelerator (E) [hereinafter, frequently referred to as “component (E)”] and a flame retardant (F) [hereinafter, frequently referred to as “component (F)”]. By virtue of containing these components, a laminate obtained using the resultant resin composition can be further improved in various properties.
- For example, an appropriate inorganic filler (D) optionally incorporated in the resin composition of the present invention can improve low thermal expansion coefficient, high modulus of elasticity, heat resistance and flame retardancy. An appropriate curing accelerator (E) incorporated in the resin composition can improve the curability of the resin composition and therefore can improve high frequency properties, heat resistance, adhesion to conductor, modulus of elasticity and glass transition temperature. Further, a flame retardant (F) and optionally a flame retardant promoter incorporated in the resin composition can improve the flame retardancy of the composition.
- The component (D) is not specifically limited, but examples thereof include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (calcined clay, etc.), talc, aluminum borate, aluminum borate, silicon carbide, etc. These may be used individually or in combination. Among these, from the viewpoint of thermal expansion coefficient, modulus of elasticity, heat resistance and flame retardancy, the component may be silica, alumina, mica or talc, or may be silica or alumina, or maybe silica. Examples of silica include a precipitated silica produced according to a wet method and having a high water content, and a dry-method silica produced according to a dry method and containing little bound water, and further, the dry-method silica includes ground silica, fumed silica and molten silica (molten spherical silica) as grouped depending on the difference in the production method.
- With respect to the shape and the particle diameter of the inorganic filler (D), there is no particular limitation, but, for example, the particle size may be 0.01 to 20 μm, or may be 0.1 to 10 μm. The term “particle diameter” used here indicates an average particle diameter, which corresponds to a particle diameter determined at a point of 50% volume in a cumulative frequency distribution curve obtained from the particle diameters when the whole volume of the particles is taken as 100%. The particle diameter can be measured by means of a particle size distribution measurement apparatus using a laser diffraction scattering method or the like.
- In the case where the component (D) is used, the content ratio of the component (D) in the resin composition is not specifically limited, but from the viewpoint of thermal expansion coefficient, modulus of elasticity, heat resistance and flame retardancy, the content ratio of the component (D) in the resin composition may be 3 to 65% by volume, or may be 5 to 60%, or may be 15 to 55% by volume. When the content ratio of the component (D) in the resin composition falls within the above range, better curability, formability and chemical resistance tend to be attained.
- In addition, in the case where the component (D) is used, if desired, a coupling agent may be used together with it for the purpose of improving the dispersibility of the component (D) and improving the adhesion between the component (D) and the organic component in the resin composition. The coupling agent is not specifically limited, and for example, a silane coupling agent or a titanate coupling agent may be adequately selected and used. One alone or two or more kinds of coupling agents may be used either singly or as combined. The amount of the coupling agent to be used is not also specifically limited, and for example, the amount may be 0.1 to 5 parts by mass relative to 100 parts by mass of the component (D), or may be 0.5 to 3 parts by mass. Within the range, various properties can be prevented from degrading and the characteristics by the use of the component (D) tend to be effectively exhibited.
- In the case where a coupling agent is used, a system of using an inorganic filler that has been previously surface-treated in dry or wet with a coupling agent may be employed, but not a so-called integral blending system where the component (D) is first incorporated in the resin composition and then a coupling agent is added thereto. Employing the former system promotes effective expression of the characteristics of the component (D).
- In the case where the component (D) is used in the present invention, if desired, the component (D) may be previously dispersed in an organic solvent to be a slurry for the purpose of improving the dispersibility of the component (D) in the resin composition. The organic solvent to be used in forming the component (D) into a slurry is not specifically limited, and for example, the organic solvents exemplified hereinabove in the production step for the polyphenylene ether compound (A″) are applicable. One alone or two or more kinds of these may be used either singly or as combined. Among these, from the viewpoint of dispersibility, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone may be selected. The solid content (nonvolatile content) concentration of the slurry is not specifically limited, but for example, from the viewpoint of precipitation and dispersion performance of the inorganic filler (D), the concentration may be 50 to 80% by mass, or may be 60 to 80% by mass.
- In the case where the component (E) is contained in the resin composition of the present invention, a suitable component (E) may be used in accordance with the kind of the component (B) to be used.
- In the case where an epoxy resin is used as the component (B), examples of the component (E) include imidazole compounds and derivatives thereof; tertiary mine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenyl phosphine, etc. One alone or two or more kinds of these may be used either singly or as combined. Among these, from the viewpoint of heat resistance, glass transition temperature and storage stability, imidazole compounds and derivatives thereof or phosphorus compounds may be used. Examples of the imidazole compounds include methylimidazole, phenylimidazole, isocyanate-masked imidazole (for example, addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole, etc.) and others, and isocyanate-masked imidazole may be selected.
- Examples of the component (E) in the case where an isocyanate resin is used as the component (B) include imidazole compounds and derivatives thereof; carboxylates with manganese, cobalt, zinc or the like; organic metal compounds such as acetylacetone complexes with a transition metal of manganese, cobalt, zinc or the like, etc. One alone or two or more kinds of these may be used either singly or as combined. Among these, from the viewpoint of heat resistance, glass transition temperature and storage stability, organic metal compounds may be used.
- Examples of the component (E) in the case where a maleimide compound is used as the component (B) include acidic catalysts such as p-toluenesulfonic acid, etc.; amine compounds such as triethylamine, pyridine, tributylamine, etc.; imidazole compounds such as methylimidazole, phenylimidazole, isocyanate-masked imidazole (for example, addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole); tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenyl phosphine, etc.; organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, α,α′-bis(t-butylperoxy)diisopropylbenzene, etc.; carboxylates with manganese, cobalt, zinc or the like, etc. One alone or two or more kinds of these may be used either singly or as combined. Among these, from the viewpoint of heat resistance, glass transition temperature and storage stability, imidazole compounds, organic peroxides and carboxylates may be used; or from the viewpoint of heat resistance, glass transition temperature, modulus of elasticity and thermal expansion coefficient, an imidazole compound may be used in combination with an organic peroxide or a carboxylate. Among organic peroxides, α,α′-bis(t-butylperoxy)diisopropylbenzene may be selected, and among carboxylates, manganese naphthenate may be selected.
- In the case where the component (E) is contained in the resin composition of the present invention, the content ratio of the component (E) is not specifically limited, but for example, the ratio may be 0.01 to 10 parts by mass relative to 100 parts by mass of the sum total of the components (A) and the component (B) in the present invention, or may be 0.01 to 5 parts by mass. Using the component (E) in the range tends to secure better heat resistance and storage stability.
- The component (F) includes phosphorus flame retardants, metal hydrates, halogen flame retardants, etc. From the viewpoint of environmental issues, phosphorus flame retardants and metal hydrates may be used. One alone or two or more kinds of flame retardants (F) may be used either singly or as combined.
- The phosphorus flame retardant for use herein is not specifically limited and may be any ordinary flame retardant containing a phosphorus atom, including inorganic phosphorus flame retardants and organic phosphorus flame retardants. From the viewpoint of environmental issues, those not containing a halogen atom may be selected. From the viewpoint of high frequency properties (low dielectric constant, low dielectric dissipation factor), adhesion to conductor, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy, organic phosphorus flame retardants may be used.
- Examples of the inorganic phosphorus flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, etc.; inorganic nitrogen-containing phosphorus compounds such as phosphoric amide, etc.; phosphoric acid; phosphine oxide, etc.
- Examples of the organic phosphorus flame retardants include aromatic phosphates, monosubstituted phosphonic diesters, disubstituted phosphinates, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, etc. Among these, aromatic phosphate compounds, and metal salts of disubstituted phosphinic acids may be selected. Here, metal salts may be any of lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts, or may be aluminum salts. Among the organic phosphorus flame retardants, aromatic phosphates may be selected.
- Examples of the aromatic phosphates include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 1,3-phenylenebis(di-2,6-xylenyl phosphate), bisphenol A bis(diphenyl phosphate), 1,3-phenylenebis(diphenyl phosphate), etc.
- Examples of the monosubstituted phosphonic diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate, etc.
- Examples of the disubstituted phosphinates include phenyl diphenylphosphinate, methyl diphenylphosphinate, etc.
- Metal salts of disubstituted phosphinic acids include metal salts of dialkylphosphinic acids, metal salts of diallylphosphinic acids, metal salts of divinylphosphinic acids, metal salts of diarylphosphinic acids, etc. These metal salts may be any of lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts, and aluminum salts may be selected.
- Examples of the organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis(2-allylphenoxy)phosphazene, dicresylphosphazene, etc.; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; melam polyphosphate, etc.
- The cyclic organic phosphorus compounds include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.
- Among these, at least one may be selected from aromatic phosphates, metal salts of disubstituted phosphinic acids and cyclic organic phosphorus compounds, or at least one may be selected from metal salts of disubstituted phosphinic acids and cyclic organic phosphorus compounds, or a metal salt of a disubstituted phosphinic acid and a cyclic organic phosphorus compound may be used in combination. In particular, the metal salt of a disubstituted phosphinic acid may be a metal salt of a dialkylphosphinic acid, or may be an aluminum salt of a dialkylphosphinic acid. The cyclic organic phosphorus compound may be 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phsophaphenanthrene-10-oxide.
- In the case where a metal salt of a disubstituted phosphinic acid and a cyclic organic phosphorus compound are used in combination, the blend ratio of the metal salt of a disubstituted phosphinic acid to the cyclic organic phosphorus compound [metal salt of disubstituted phosphinic acid/cyclic organic phosphorus compound] may be 0.6 to 2.5 by mass, or may be 0.9 to 2, or may be 1 to 2, or may be 1.2 to 2.
- The aromatic phosphates may be aromatic phosphates represented by the following general formula (F-1) or (F-2), and the metal salts of a disubstituted phosphinic acid may be metal salts of a disubstituted phosphinic acid represented by the following general formula (F-3).
- In the formulae, RF1 to RF5 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom. e and f each independently represent an integer of 0 to 5, g, h and i each independently represent an integer of 0 to 4.
- RF6 and RF7 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms. M represents a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom, or a zinc atom. m1 represents an integer of 1 to 4.
- The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom that RF1 to RF5 represent include the same ones as those of R1 in the above-mentioned general formula (I).
- e and f each may be an integer of 0 to 2, or may be 2. g, h and i each may be an integer of 0 to 2, or may be 0 or 1, or may be 0.
- The aliphatic hydrocarbon group having 1 to 5 carbon atoms that RF6 and RF7 represent include the same ones as those of R1 in the general formula (I). The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and may be an ethyl group.
- Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms that RF6 and RF7 represent include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, etc. The aromatic hydrocarbon group may be an aromatic hydrocarbon group having 6 to 10 carbon atoms.
- m1 represents a valence of a metal ion, that is, it varies within a range of 1 to 4 depending on the kind of M.
- M may be an aluminum atom. When M is an aluminum atom, m1 is 3.
- Examples of the metal hydrate include aluminum hydroxide hydrate, magnesium hydroxide hydrate, etc. One alone or two or more kinds of these may be used either singly or as combined. The metal hydroxide may correspond to an inorganic filler, but in the case of a material that imparts flame retardancy, this is grouped in a flame retardant.
- The halogen flame retardant includes a chlorine-based flame retardant, a bromine-based flame retardant, etc. Examples of the chlorine-based flame retardant include paraffin chloride, etc. Examples of the bromine-based flame retardant include brominated epoxy resins such as brominated bisphenol A-type epoxy resin, brominated phenol-novolak-type epoxy resin, etc.; brominated addition-type flame retardants such as hexabromobenzene, pentabromotoluene, ethylenebis(pentabromophenyl), ethylenebis-tetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, etc. (here, “addition-type” means that bromine has been introduced into the polymer in a form not chemically bonding thereto, that is, bromine has been blended in the polymer); unsaturated double bond group-containing brominated reaction-type flame retardants such as tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A-type dimethacrylate, pentabromobenzyl acrylate, styrene bromide, etc. (here, “reaction-type” means that bromine has been introduced into the polymer in a form chemically bonding thereto), etc. One alone or two or more kinds of these may be used either singly or as combined.
- In the case where a phosphorus flame retardant it used, the content ratio of the phosphorus flame retardant in the resin composition of the present invention is not specifically limited, but for example, the phosphorus atom content in the resin composition in terms of the solid content therein (sum total of the other components than the component (D)) may be 0.2 to 5% by mass, or may be 0.3 to 3% by mass. When the phosphorus atom content is 0.2% by mass or more, better flame retardancy tends to be attained. When the phosphorus atom content is 5% by mass or less, better formability, high adhesion to conductor, excellent heat resistance and high glass transition temperature tend to be attained.
- On the other hand, in the case where a halogen flame retardant is contained in the resin composition of the present invention, from the viewpoint of environmental issues and chemical resistance, the content thereof may be 20 parts by mass or less relative to 100 parts by mass of the sum total of the components (A) to (C), or may be 10 parts by mass or less, or may be 5 parts by mass or less.
- In the case where any other flame retardant than a phosphorus flame retardant and a halogen flame retardant is contained in the resin composition of the present invention, the content thereof may be, though not specifically limited thereto, 0.5 to 20 parts by mass relative to 100 parts by mass of the sum total of the components (A) to (C), or may be 1 to 15 parts by mass, or may be 1 to 10 parts by mass, or may be 1 to 6 parts by mass.
- The resin composition of the present invention may contain a flame retardant promoter, for example, an inorganic flame retardant promoter such as antimony trioxide, zinc molybdate, etc.
- When a flame retardant promoter is contained in the resin composition of the present invention, the content ratio thereof is not specifically limited, but may be, for example, 0.1 to 20 parts by mass relative to 100 parts by mass of the sum total of the component (A) and the component (B), or may be 0.1 to 10 parts by mass. Containing a flame retardant promoter in such a range, the resin composition tends to realize better chemical resistance.
- If desired, the resin composition of the present invention may adequately contain a resin material such as a known thermoplastic resin, an elastomer, etc., as well as a coupling agent, an antioxidant, a thermal stabilizer, an antistatic agent, a UV absorbent, a pigment, a colorant, a lubricant, etc. One alone or two or more kinds of these may be contained either singly or as combined. The amount of these to be used is not specifically limited.
- The resin composition of the present invention may contain an organic solvent, from the viewpoint of easy handleability through dilution and from the viewpoint of easy production of prepreg to be mentioned hereinunder.
- Examples of the organic solvent include, though not specifically limited thereto, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc.; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ether solvents such as tetrahydrofuran, etc.; aromatic solvents such as toluene, xylene, mesitylene, etc.; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.; sulfur atom-containing solvents such as dimethylsulfoxide, etc.; ester solvents such as y-butyrolactone, etc.
- Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents or nitrogen atom-containing solvents may be used, or acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone may be used, or methyl ethyl ketone may be used.
- One alone or two or more kinds of organic solvents may be used either singly or as combined.
- The content of the organic solvent in the resin composition of the present invention is not specifically limited, and the solid concentration may be 30 to 90% by mass, or may be 40 to 80% by mass, or may be 40 to 70% by mass, or may be 40 to 60% by mass. The resin composition whose solid concentration falls within the range secures good handleability and penetrability into substrate, and betters the appearance of prepreg to be produced, and the solid concentration of resin in the prepreg to be mentioned below can be readily controlled, therefore facilitating production of a prepreg having a desired thickness.
- The above-mentioned components (A) to (C), and the other optional components to be combined, and optionally an organic solvent are mixed in a known method to produce the resin composition of the present invention. In this stage, the components may be dissolved or dispersed with stirring. The conditions for the mixing order, the temperature, the time and others are not specifically limited, and may be defined in any desired manner.
- The glass transition temperature of the laminate formed with the resin composition of the present invention is not specifically limited, but from the viewpoint of good soldering heat resistance and through-hole interconnection reliability, as well as excellent workability in producing electronic parts and others, the temperature is preferably 200° C. or higher. There is no specific limitation in point of the upper limit of the glass transition temperature, and for example, the temperature may be 1,000° C. or lower, or may be 500° C. or lower, or may be 300° C. or lower, or may be 240° C. or lower.
- The thermal expansion coefficient (in Z direction, not higher than Tg) of the laminate formed with the resin composition of the present invention is not specifically limited, but from the viewpoint of preventing the laminate from warping, the coefficient is preferably 45 ppm/° C. or less, more preferably 40 ppm/° C. or less. The lower limit of the thermal expansion coefficient is, though not specifically limited thereto, generally 30 ppm/° C. or more, preferably 35 ppm/° C. or more.
- The glass transition temperature and the thermal expansion coefficient are values measured according to IPC Standards, as described in the section of Examples.
- The dielectric constant and the dielectric dissipation factor of the laminate formed with the resin composition of the present invention are not specifically limited. From the viewpoint of favorable use in a high frequency zone, the dielectric constant at 10 GHz is preferably smaller, and may be 3.85 or less, or may be 3.75 or less, or may be 3.65 or less. The lower limit of the dielectric constant is not specifically limited, and may be, for example, 0.5 or more, or may be 1 or more, or may be 3 or more, or may be 3.4 or more.
- The dielectric dissipation factor is preferably smaller, and may be 0.007 or less, or may be 0.006 or less, or may be 0.005 or less. The lower limit of the dielectric dissipation factor is not specifically limited and is preferably smaller, and may be, for example, 0.0001 or more, or may be 0.002 or more, or may be 0.004 or more.
- The dielectric constant and the dielectric dissipation factor are values according to JPCA-TM001 (Triplate-line resonator method) as described in the section of Examples.
- The present invention also provides a prepreg containing the resin composition of the present invention and a sheet-form fiber-reinforced substrate. The prepreg is formed using the resin composition of the present invention and a sheet-form fiber-reinforced substrate, and more specifically, the prepreg is formed by impregnating or coating a sheet-form fiber reinforced substrate with the resin composition of the present invention, and drying the substrate. More specifically, for example, the substrate is dried by heating in a drying oven generally at a temperature of 80 to 200° C. for 1 to 30 minutes to semi-cure the resin (into a B-stage), thereby producing the prepreg of the present invention. The amount of the resin composition to be used may be defined so that the resin composition-derived solid concentration in the dried prepreg could be 30 to 90% by mass. When the solid content is controlled to fall within the range, the laminate to be obtained using the resultant prepreg can achieve excellent formability.
- As the sheet-form fiber reinforced substrate for the prepreg, a known substrate used in a laminate for various electrically insulating materials is used. Examples of the materials for the sheet-form reinforced substrate include inorganic fibers of E glass, D glass, S glass, Q glass or the like; organic fibers of polyimide, polyester, tetrafluoroethylene or the like; mixtures thereof, etc. These sheet-form reinforced substrate may have, for example, a form of woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, etc. With respect to the thickness of the sheet-form fiber reinforced substrate, there is no particular limitation, and, for example, the substrate having a thickness of about 0.02 to 0.5 mm can be used. Further, the substrate having a surface treated with a coupling agent or the like or having a mechanically opening treated substrate can be used from the viewpoint of impregnation performance with the resin composition, and from the viewpoint of heat resistance, moisture absorption resistance, and processability of the laminate formed with the substrate.
- As the method of impregnating or coating the sheet-form reinforced substrate with the resin composition, a hot melt method or a solvent method to be mentioned below may be employed.
- In the hot melt method, an organic solvent is not contained in the resin composition, and the method is (1) a method of once applying the composition onto a releasable sheet, and laminating it on a sheet-form reinforced substrate, or (2) a method of directly applying the resin composition to a sheet-form reinforced substrate using a die coater.
- On the other hand, the solvent method is a method of adding an organic solvent to the resin composition, and immersing a sheet-form reinforced substrate in the resultant resin composition so that the sheet-form reinforced substrate could be impregnated with the resin composition, and thereafter drying it.
- The laminate of the present invention contains the prepreg of the present invention and a metal foil. The laminate of the present invention is formed using the prepreg of the present invention and a metal foil, and more specifically, the laminate is formed by arranging a metal foil on one surface or both surfaces of one prepreg, or by arranging a metal foil on one surface of both surfaces of a multilayer prepreg prepared by layering two or more prepregs of the present invention, and thereafter molding the resultant structure under heat and pressure.
- Not specifically limited, the metal for the metal foil may be any one usable for electrically insulating materials, but from the viewpoint of electroconductivity, the metal may be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements, or may be copper or aluminium, or may be copper.
- The condition for thermal pressure forming is not specifically limited. For example, the temperature may be 100° C. to 300° C., the pressure may be 0.2 to 10.0 MPa, and the time may be 0.1 to 5 hours. For thermal pressure forming, a method of using a vacuum press or the like to keep a vacuum state for 0.5 to 5 hours may be employed.
- The multilayer printed wiring board of the present invention is formed using the prepreg or the laminate of the present invention. The multilayer printed wiring board of the present invention can be produced using the prepreg or the laminate of the present invention by performing circuit formation processing and bonding processing for forming a multilayer by perforating, metal plating, etching for a metal foil or the like according to a known method.
- The resin composition, the resin film, the prepreg, the metal-clad laminate and the multilayer printed wiring board of the present invention are favorably used in electronic devices working with high frequency signals of 1 GHz or more, and are especially favorably used in electronic devices working with high frequency signals of 10 GHz or more.
- Hereinabove, the preferred embodiments of the present invention were described, but these embodiments are examples used for describing the present invention, and these embodiments should not be construed as limiting the scope of the present invention. The present invention can be practiced in various modes different from the above-described embodiments as long as the polyphenylene ether derivative and the like of the present invention can be obtained.
- Hereinbelow, the present invention will be described in detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention.
- Toluene, polyphenylene ether having a number average molecular weight of about 16,000, and p-aminophenol were charged into a glass flask container having a capacity of 2 liters and being equipped with a thermometer, a reflux condenser, and a stirrer and being capable of heating and cooling the contents of the flask, and dissolved with stirring at 90° C.
- After confirming the dissolution visually, t-butylperoxyisopropyl monocarbonate and manganese naphthenate were added to the resultant solution to perform a reaction at a solution temperature of 90° C. for 4 hours, and then cooled to 70° C. to give a polyphenylene ether compound (A′) having a primary amino group at the end of the molecule. A small portion of the resultant reaction solution was taken and subjected to GPC (polystyrene-equivalent measurement, eluent: tetrahydrofuran). As a result, it was found that the peak derived from p-aminophenol disappeared and the polyphenylene ether compound had a number average molecular weight of about 9,200. Further, another small portion of the reaction solution was taken and dropwise added to a methanol/benzene mixed solvent (mass ratio in the mixed solvent: 1:1) to cause reprecipitation, and the resultant purified solid material was subjected to FT-IR measurement. The result of the FT-IR measurement confirmed that a peak derived from a primary amino group appeared at around 3,400 cm−1.
- Here, the number average molecular weight was measured by gel permeation chromatography (GPC) in which standard polystyrenes were used for obtaining a molecular weight conversion calibration curve. The calibration curve was obtained using standard polystyrenes: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [trade name, manufactured by Tosoh Corp.]) and approximated to a cubic equation. Conditions for GPC are shown below.
- Apparatus: (Pump: L-6200 Model [manufactured by Hitachi High-Technologies Corporation]),
- (Detector: L-3300 Model RI [manufactured by Hitachi High-Technologies Corporation]),
- (Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation])
- Column: Guard column; TSK Guard column HHR-L+Column; TSK gel-G4000HHR+TSK gel-G2000HHR (trade name, each of which is manufactured by Tosoh Corp.)
- Column size: 6.0×40 mm (guard column), 7.8×300 mm (column)
- Eluent: Tetrahydrofuran
- Concentration of a sample: 30 mg/5 mL
- Amount of a sample per injection: 20 μL
- Flow rate: 1.00 mL/minute
- Temperature for measurement: 40° C.
- Then, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide and propylene glycol monomethyl ether were added to the above-obtained reaction solution, and the temperature of the resultant mixture was increased while stirring, and, while maintaining the temperature at 120° C., a reaction was conducted for 4 hours, followed by cooling and 200-mesh filtration, to produce a polyphenylene ether derivative (A-1). A small portion of the resultant reaction solution was taken and subjected to reprecipitation in the same manner as mentioned above, and the resultant purified solid material was subjected to FT-IR measurement. The result of the FT-IR measurement confirmed that the peak at around 3,500 cm−1 derived from a primary amino group disappeared and a peak of a carbonyl group appeared at 1,700 to 1,730 cm−1. Further, the solid material was subjected to GPC measurement (under the same conditions as mentioned above). As a result, the number average molecular weight was found to be about 9,400.
- The amount of each component used is shown in Table 1.
- A polyphenylene ether derivative (A-2) was produced in the same manner as in Production Example A-1 except that, instead of 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane was used, and the individual components with the formulation shown in Table 1 were used. The polyphenylene ether derivative (A-2) had a number average molecular weight of about 9,400.
- The amount of each component used is shown in Table 1.
- A polyphenylene ether derivative (A-3) was produced in the same manner as in Production Example A-1 except that, instead of 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 1,6-bismaleimido-(2,2,4-trimethyl)hexane was used, and the individual components with the formulation shown in Table 1 were used. The polyphenylene ether derivative (A-3) had a number average molecular weight of about 9,500.
- The amount of each component used is shown in Table 1.
- A polyphenylene ether derivative (A-4) was produced in the same manner as in Production Example A-2 except that, instead of p-aminophenol, m-aminophenol was used. The polyphenylene ether derivative (A-4) had a number average molecular weight of about 9,400.
- The amount of each component used is shown in Table 1.
- A polyphenylene ether derivative (A-5) was produced in the same manner as in Production Example A-2 except that p-aminophenol and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane were used and the individual components with the formulation shown in Table 1 were used. The polyphenylene ether derivative (A-5) had a number average molecular weight of about 5,000.
- The amount of each component used is shown in Table 1.
- A polyphenylene ether derivative (A-6) in Production Example A-6 was produced in the same manner as in Production Example A-2 except that p-aminophenol and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane were used and the individual components with the formulation shown in Table 1 were used. The polyphenylene ether derivative (A-6) had a number average molecular weight of about 12,000.
- The amount of each component used is shown in Table 1.
-
TABLE 1 Production of Component (A) Production Example A-1 A-2 A-3 A-4 A-5 A-6 Polyphenylene Ether PPO640 100 100 100 100 100 100 Number Average Molecular Weight about about about about about about 16,000 16,000 16,000 16,000 16,000 16,000 Aminophenol Compound (XIII) p-aminophenol 1.35 1.35 1.35 3.8 0.8 m-aminophenol 1.35 Bismaleimide Compound (XV) BMI-5100 5.5 BMI-4000 7.2 7.2 20 4.3 BMI-TMH 4 Reaction Catalyst Perbutyl I 2 2 2 2 2 2 manganese 0.15 0.15 0.15 0.15 0.15 0.15 naphthenate Organic Solvent toluene 190 190 190 190 200 200 propylene glycol 12 15 9 15 40 8 monomethyl ether Number Average Molecular Weight of 9,400 9,400 9,500 9,400 5,000 12,000 Polyphenylene Ether Derivative (A) Unit of amount: part by mass - Abbreviations of the materials in Table 1 are as follows.
- PPO640: polyphenylene ether (manufactured by SABIC Innovative Plastics Japan LLC.), number average molecular weight=about 16,000, trade name
- p-Aminophenol: manufactured by Ihara Chemical Industry Co., Ltd.
- m-Aminophenol: manufactured by Kanto Chemical Co., Ltd.
- BMI-5100: 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, trade name (manufactured by Daiwa Kasei Industry Co., Ltd.)
- BMI-4000: 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, trade name (manufactured by Daiwa Kasei Industry Co., Ltd.)
- BMI-TMH: 1,6-bismaleimido-(2,2,4-trimethyl)hexane, trade name (manufactured by Daiwa Kasei Industry Co., Ltd.)
- Perbutyl (registered trademark) I: t-butylperoxyisopropyl monocarbonate (manufactured by NOF Corporation)
- Manganese naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.)
- Toluene (manufactured by Kanto Chemical Co., Ltd.)
- Propylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.)
- 2,2-Bis(4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane and propylene glycol monomethyl ether were charged into a glass flask container having a capacity of 1 liter and being equipped with a thermometer, a reflux condenser, and a stirrer and being capable of heating and cooling the contents of the flaks, and, while maintaining the temperature thereof at 120° C. and stirring, the resultant mixture was reacted for 3 hours, and then cooled and filtered through a 200-mesh filter to produce a polyaminobismaleimide compound (B-1).
- The amount of each component used is shown in Table 2.
- A polyaminobismaleimide compound (B-2) was produced in the same manner as in Production Example B-1 except that, instead of 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline was used in the amounts shown in Table 2.
- The amount of each component used is shown in Table 2.
- A polyaminobismaleimide compound (B-3) was produced in the same manner as in Production Example B-1 except that, instead of 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane and 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide and 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline were used in the amounts shown in Table 2.
- The amount of each component used is shown in Table 2.
- Toluene, 2,2-bis(4-cyanatophenyl)propane, and p-(α-cumyl)phenol were charged into a glass flask container having a capacity of 1 liter and being equipped with a thermometer, a reflux condenser, and a stirrer and being capable of heating and cooling the contents of the flaks. After the dissolution of the solid material was confirmed visually, manganese naphthenate as a reaction catalyst was added to the solution with stirring at 110° C. to perform a reaction for 3 hours, followed by cooling and 200-mesh filtration, to produce a phenol-modified cyanate prepolymer solution (B-4)
- The amount of each component used is shown in Table 2.
-
TABLE 2 Production of Component (B) Production Example B-1 B-2 B-3 B-4 Polymaleimide BMI-5100 50 Compound(a) BMI-4000 100 100 50 Aromatic Diamine BAPP 15 Compound (b) Bisaniline-P 12 Bisaniline-M 14 Cyanate Resin BADCy 100 Monophenol p-(α-cumyl)phenol 1.55 Compound Reaction manganese 0.03 Catalyst naphthenate Organic toluene 44 Solvent propylene glycol 50 48 50 monomethyl ether Unit of amount: part by mass - Abbreviations of the materials in Table 2 are as follows.
- BMI-5100: 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, trade name, (manufactured by Daiwa Kasei Industry Co., Ltd.)
- BMI-4000: 2,2-bis(4(4-maleimidophenoxy)phenyl)propane, trade name, (manufactured by Daiwa Kasei Industry Co., Ltd.)
- BAPP: 2,2-bis(4-(4-aminophenoxy)phenyl)propane, trade name (manufactured by Wakayama Seika Kogyo Co., Ltd.)
- Bisaniline-P: 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline, trade name (manufactured by Mitsui Chemicals, Inc.)
- Bisaniline-M: 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisaniline, trade name (manufactured by Mitsui Chemicals, Inc.)
- BADCy: Primaset (registered trademark) BADCy, 2,2-bis(4-cyanatophenyl)propane (manufactured by Lonza Group AG)
- p-(α-cumyl)phenol (manufactured by Mitsui Fine Chemicals, Inc.)
- Manganese naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.)
- The components shown in Tables 3 to 7 were stirred and mixed according to the formulation of blending quantities (unit: part by mass) shown in Tables 3 to 7 at room temperature or with heating at 50 to 80° C. to prepare resin compositions having a solid content (nonvolatile component) concentration of 40 to 60% by mass.
- Here, the resin composition (excluding inorganic filler) generally has a density of 1.20 to 1.25 g/cm3, and the inorganic filler used has a density of 2.2 to 3.01 g/cm3. Therefore, when 80 parts by mass of the inorganic filler is incorporated, relative to 100 parts by mass of the resin composition (excluding inorganic filler), the amount of the inorganic filler incorporated is about 30 to 34% by volume.
- The resin compositions obtained in Examples and Comparative Examples were analyzed and evaluated according to the methods mentioned below. The results are shown in Tables 3 to 7.
- With respect to the resin compositions obtained in the above Example and those dried at 160° C. for 10 minutes to remove the organic solvent therefrom, the appearance thereof was visually examined, and the compatibility was evaluated (whether macroscopic phase separation or unevenness was present or not) in accordance with the criteria shown below.
- A: Macroscopic phase separation or unevenness is not present.
- B: Macroscopic phase separation or unevenness is present.
- The resin composition obtained in each Example was applied to glass cloth having a thickness of 0.1 mm (E glass, manufactured by Nitto Boseki Co., Ltd.), and then dried by heating at 160° C. for 7 minutes to prepare a prepreg having a resin content of about 54% by mass. 6 sheets of the prepared prepreg were stacked on one another, and low profile copper foils having a thickness of 18 μm (FV-WS, M-side Rz: 1.5 μm; manufactured by The Furukawa Electric Co., Ltd.) were disposed respectively on the top and bottom of the resultant laminate so that the M-side of each copper foil was in contact with the laminate, and subjected to hot pressing under conditions such that the temperature was 230° C. (200° C. in Comparative Examples 5 and 6), the pressure was 3.9 MPa, and the time was 180 minutes to prepare a double-sided copper-clad laminate (thickness: 0.8 mm).
- The appearance of the above-obtained prepreg was examined. The appearance was visually examined, and the prepreg was evaluated according to the criteria shown below.
- A: Nothing wrong on appearance.
- C: The prepreg surface has some unevenness, streak, foaming, phase separation and the like, and lacks surface smoothness.
- With respect to the above-obtained copper-clad laminate, the formability, the dielectric properties, the copper foil peel strength, the glass transition temperature, the thermal expansion coefficient, the soldering heat resistance, and the flame retardancy thereof were evaluated. The methods for evaluation of the properties of the copper-clad laminate are as described below.
- The appearance of the laminate having etched copper foils on both sides was examined to evaluate the formability. The formability was visually evaluated, and the laminate was evaluated according to the following criteria.
- A: Nothing wrong on appearance.
- C: The laminate has some unevenness, streak, thinned area, voids or the like, and lacks surface smoothness.
- The copper-clad laminate was immersed in a copper etchant, 10 mass % solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Corporation) to remove the copper foil, and a test piece of 2 mm×85 mm was cut out of the resultant substrate for evaluation.
- The test piece was tested according to JPCA-TM001 (Triplate-line resonator method) at 10 GHz band.
- Copper foil peel strength was measured in accordance with JIS-C-6481 (1996) to thereby determine the adhesion to conductor.
- A soldering heat resistance was evaluated using a 50 mm square test specimen having etched copper foils on both sides as follows. 3 specimens in a dry state and 3 specimens, which had been treated in a pressure cooker test (PCT) apparatus (conditions: 121° C., 2.2 atm.) for a predetermined period of time (1, 3, or 5 hours), were immersed in molten solder at 288° C. for 20 seconds, and then the appearance of each of the resultant specimens was visually examined. The figures shown in the tables mean, among the 3 specimens obtained after immersed in the solder, the number of the specimen or specimens in which a defect, such as the occurrence of blistering or measling, was not recognized in the laminate.
- Five mm square test pieces that had been etched to remove the copper foil from both sides thereof were analyzed in accordance with IPC (The Institute for Interconnecting and Packaging Electronic Circuits) Standards using a thermomechanical analyzer (TMA) [manufactured by TA Instruments Japan Corporation, Q400 (Model Number)] to measure the glass transition temperature (Tg) and the thermal expansion coefficient (linear expansion coefficient, thickness direction, temperature range: 30 to 150° C.) thereof.
- The copper-clad laminate was immersed in a copper etchant, 10 mass % solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Corporation) to remove the copper foil, and a test piece having a length of 127 mm and a width of 12.7 mm was cut out of the resultant substrate for evaluation. The test piece was tested according to the test method (V method) of UL94 to evaluate the flame retardancy thereof.
- Namely, the lower edge of the test piece held vertically was exposed to 20-mm flame for 10 seconds, twice in every test. The evaluation was carried out according to the criteria in the V method of UL94.
-
TABLE 3 Example 1 2 3 4 Polyphenylene Ether Polyphenylene Ether Derivative (A-1) solid concentration 35% by mass 100 100 100 100 Derivative (A) Polyphenylene Ether Derivative (A-2) solid concentration 35% by mass Polyphenylene Ether Derivative (A-3) solid concentration 35% by mass Polyphenylene Ether Derivative (A-4) solid concentration 35% by mass Polyphenylene Ether Derivative (A-5) solid concentration 35% by mass Polyphenylene Ether Derivative (A-6) solid concentration 35% by mass Thermosetting Resin BMI-4000 (bismaleimide) 88 (B) NC-3000H (epoxy resin) 35 NC-7000L (epoxy resin) 26 Polyaminobismaleimide Compound (B-1) solid concentration 70% by mass 126 Polyaminobismaleimide Compound (B-2) solid concentration 70% by mass Polyaminobismaleimide Compound (B-3) solid concentration 70% by mass Phenol-Modified Cyanate Prepolymer (B-4) solid concentration 70% by mass Styrenic Thermoplastic Tuftec H1043 53 47 56 53 Elastomer (C) Inorganic Filler (D) SC-2050 KNK solid concentration 70% by mass 237 161 158 238 Curing Accelerator (E) Perbutyl-P 1.8 1.8 G-8009L solid concentration 50% by mass 0.9 0.7 0.26 0.9 Manganese Naphthenate Flame Retardant (F) OP-935 12 10 10 12 HCA-HQ 8 7 7 8 Organic Solvent Toluene 106 69 Methyl ethyl ketone 51 51 Resin Composition Compatibility with solvent A A A A after solvent evaporation A A A A Prepreg Appearance A A A A Laminate Formability A A A A Dielectric Constant 10 GHz 3.6 3.8 3.7 3.5 Dielectric Dissipation Factor 10 GHz 0.0047 0.0056 0.0055 0.0046 Copper Foil Peel Strength (kN/m) 0.62 0.69 0.68 0.66 Soldering Heat Resistance ordinary state 3 3 3 3 after PCT-1 hr treatment 3 3 3 3 after PCT-3 hr treatment 3 3 3 3 after PCT-5 hr treatment 3 3 3 3 Glass Transition Temperature (° C.) 212 221 223 209 Thermal Expansion Coefficient (ppm/° C.) 38 36 38 41 Flame Retardancy V-0 V-0 V-1 V-0 Example 5 6 7 8 Polyphenylene Ether Polyphenylene Ether Derivative (A-1) solid concentration 35% by mass 100 100 100 Derivative (A) Polyphenylene Ether Derivative (A-2) solid concentration 35% by mass 100 Polyphenylene Ether Derivative (A-3) solid concentration 35% by mass Polyphenylene Ether Derivative (A-4) solid concentration 35% by mass Polyphenylene Ether Derivative (A-5) solid concentration 35% by mass Polyphenylene Ether Derivative (A-6) solid concentration 35% by mass Thermosetting Resin BMI-4000 (bismaleimide) (B) NC-3000H (epoxy resin) NC-7000L (epoxy resin) Polyaminobismaleimide Compound (B-1) solid concentration 70% by mass 126 Polyaminobismaleimide Compound (B-2) solid concentration 70% by mass 126 Polyaminobismaleimide Compound (B-3) solid concentration 70% by mass 126 Phenol-Modified Cyanate Prepolymer (B-4) solid concentration 70% by mass 100 Styrenic Thermoplastic Tuftec H1043 53 53 70 53 Elastomer (C) Inorganic Filler (D) SC-2050 KNK solid concentration 70% by mass 238 238 234 237 Curing Accelerator (E) Perbutyl-P 1.8 1.8 1.8 G-8009L solid concentration 50% by mass 0.9 0.9 0.3 0.9 Manganese Naphthenate 0.015 Flame Retardant (F) OP-935 12 12 12 12 HCA-HQ 8 8 7 8 Organic Solvent Toluene 69 69 72 69 Methyl ethyl ketone Resin Composition Compatibility with solvent A A A A after solvent evaporation A A A A Prepreg Appearance A A A A Laminate Formability A A A A Dielectric Constant 10 GHz 3.6 3.6 3.7 3.8 Dielectric Dissipation Factor 10 GHz 0.0048 0.0047 0.0050 0.0051 Copper Foil Peel Strength (kN/m) 0.60 0.64 0.61 0.65 Soldering Heat Resistance ordinary state 3 3 3 3 after PCT-1 hr treatment 3 3 3 3 after PCT-3 hr treatment 3 3 3 3 after PCT-5 hr treatment 3 3 3 3 Glass Transition Temperature (° C.) 212 215 216 215 Thermal Expansion Coefficient (ppm/° C.) 44 38 41 43 Flame Retardancy V-0 V-0 V-1 V-0 Example 9 10 11 12 Polyphenylene Ether Polyphenylene Ether Derivative (A-1) solid concentration 35% by mass Derivative (A) Polyphenylene Ether Derivative (A-2) solid concentration 35% by mass Polyphenylene Ether Derivative (A-3) solid concentration 35% by mass 100 Polyphenylene Ether Derivative (A-4) solid concentration 35% by mass 100 Polyphenylene Ether Derivative (A-5) solid concentration 35% by mass 100 Polyphenylene Ether Derivative (A-6) solid concentration 35% by mass 100 Thermosetting Resin BMI-4000 (bismaleimide) (B) NC-3000H (epoxy resin) NC-7000L (epoxy resin) Polyaminobismaleimide Compound (B-1) solid concentration 70% by mass 126 126 Polyaminobismaleimide Compound (B-2) solid concentration 70% by mass 126 Polyaminobismaleimide Compound (B-3) solid concentration 70% by mass 126 Phenol-Modified Cyanate Prepolymer (B-4) solid concentration 70% by mass Styrenic Thermoplastic Tuftec H1043 53 53 53 53 Elastomer (C) Inorganic Filler (D) SC-2050 KNK solid concentration 70% by mass 237 237 237 237 Curing Accelerator (E) Perbutyl-P 1.8 1.8 1.8 1.8 G-8009L solid concentration 50% by mass 0.9 0.9 0.9 0.9 Manganese Naphthenate Flame Retardant (F) OP-935 12 12 12 12 HCA-HQ 8 8 8 8 Organic Solvent Toluene 69 69 69 69 Methyl ethyl ketone Resin Composition Compatibility with solvent A A A A after solvent evaporation A A A A Prepreg Appearance A A A A Laminate Formability A A A A Dielectric Constant 10 GHz 3.6 3.7 3.8 3.6 Dielectric Dissipation Factor 10 GHz 0.0046 0.0048 0.0046 0.0048 Copper Foil Peel Strength (kN/m) 0.69 0.64 0.68 0.69 Soldering Heat Resistance ordinary state 3 3 3 3 after PCT-1 hr treatment 3 3 3 3 after PCT-3 hr treatment 3 3 3 3 after PCT-5 hr treatment 3 3 3 3 Glass Transition Temperature (° C.) 218 208 218 211 Thermal Expansion Coefficient (ppm/° C.) 44 41 42 41 Flame Retardancy V-0 V-0 V-0 V-0 (The unit of content is part by mass. For solution, the content is in terms of solid content.) -
TABLE 4 Example 13 14 15 16 17 18 19 20 21 22 Polyphenylene Ether Polyphenylene Ether Derivative (A-1) solid concentration 35% by mass 100 100 100 100 100 100 100 100 100 100 Derivative (A) Thermosetting Resin Polyaminobismaleimide Compound (B-1) solid concentration 70% by mass 100 125 138 110 120 100 86 89 58 58 (B) Styrenic Tuftec H1043 245 53 Thermoplastic Tuftec H1051 44 Elastomer (C) Tuftec H1053 28 Tuftec H1052 21 Tuftec H1221 12 5 3 Tuftec M1911 41 Tuftec M1943 41 Inorganic Filler (D) SC-2050 KNK solid concentration 70% by mass 522 251 251 200 200 167 144 144 174 174 Curing Accelerator Perbutyl-P 1.4 1.8 1.9 1.5 1.7 1.4 1.2 1.2 0.8 0.8 (E) G-8009L solid concentration 50% by mass 0.7 0.9 1.0 0.8 0.8 0.7 0.6 0.6 0.4 0.4 Flame Retardant (F) OP-935 35 12 12 10 10 8 7 7 8 8 HCA-HQ 25 8 8 6 6 5 5 5 12 12 Organic Solvent Toluene 266 71 67 40 37 20 9 8 38 38 Methyl ethyl ketone Resin Composition Compatibility with solvent A A A A A A A A A A after solvent evaporation A A A A A A A A A A Prepreg Appearance A A A A A A A A A A Laminate Formability A A A A A A A A A A Dielectric Constant 10 GHz 3.3 3.7 3.5 3.7 3.6 3.6 3.7 3.8 3.6 3.7 Dielectric Dissipation Factor 10 GHz 0.0042 0.0045 0.0046 0.0048 0.0048 0.0049 0.0050 0.0053 0.0048 0.0049 Copper Foil Peel Strength (kN/m) 0.61 0.68 0.65 0.68 0.67 0.69 0.70 0.72 0.68 0.66 Soldering Heat Resistance ordinary state 3 3 3 3 3 3 3 3 3 3 after PCT-1 hr treatment 3 3 3 3 3 3 3 3 3 3 after PCT-3 hr treatment 3 3 3 3 3 3 3 3 3 3 after PCT-5 hr treatment 3 3 3 3 3 3 3 3 3 3 Glass Transition Temperature (° C.) 216 211 216 220 219 225 227 231 208 209 Thermal Expansion Coefficient (ppm/° C.) 46 39 38 41 43 36 32 30 41 39 Flame Retardancy V-1 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 (The unit of content is part by mass. For solution, the content is in terms of solid content.) -
TABLE 5 Example 23 24 25 26 27 28 Polyphenylene Ether Polyphenylene Ether solid concentration 100 100 100 100 100 100 Derivative (A) Derivative (A-1) 35% by mass Thermosetting Resin Polyaminobismaleimide solid concentration 58 125 57 50 50 100 (B) Compound (B-1) 70% by mass Styrenic Thermoplastic Tuftec P2000 41 Elastomer (C) Tuftec S2002 53 Tuftec S2005 25 SMA Resin EF-30 70 SMA Resin EF-80 47 245 Inorganic Filler (D) SC-2050 KNK solid concentration 165 251 142 209 175 522 70% by mass Curing Accelerator (E) Perbutyl-P 0.8 1.8 0.8 0.7 0.7 1.4 G-8009L solid concentration 0.4 0.9 0.4 0.4 0.4 0.7 50% by mass Flame Retardant (F) OP-935 8 12 7 14 12 35 HCA-HQ 5 8 4 10 8 25 Organic Solvent Toluene 32 71 16 65 41 266 Methyl ethyl ketone Resin Composition Compatibility with solvent A A A A A A after solvent evaporation A A A A A A Prepreg Appearance A A A A A A Laminate Formability A A A A A A Dielectric Constant 10 GHz 3.6 3.6 3.7 3.6 3.7 3.6 Dielectric Dissipation 10 GHz 0.0048 0.0047 0.0048 0.0047 0.0048 0.0047 Factor Copper Foil Peel Strength (kN/m) 0.69 0.67 0.65 0.69 0.64 0.67 Soldering Heat Resistance ordinary state 3 3 3 3 3 3 after PCT-1 hr treatment 3 3 3 3 3 3 after PCT-3 hr treatment 3 3 3 3 3 3 after PCT-5 hr treatment 3 3 3 3 3 3 Glass Transition 212 209 218 203 208 201 Temperature (° C.) Thermal Expansion 38 41 37 38 41 43 Coefficient (ppm/° C.) Flame Retardancy V-0 V-0 V-0 V-1 V-0 V-1 (The unit of content is part by mass. For solution, the content is in terms of solid content.) -
TABLE 6 Comparative Example 1 2 3 4 Polyphenylene Ether Polyphenylene Ether Derivative (A-1) solid concentration 35% by mass 100 100 100 100 Derivative (A) Polyphenylene Ether Derivative (A-2) solid concentration 35% by mass Polyphenylene Ether Derivative (A-3) solid concentration 35% by mass Polyphenylene Ether Derivative (A-4) solid concentration 35% by mass Polyphenylene Ether Derivative (A-5) solid concentration 35% by mass Polyphenylene Ether Derivative (A-6) solid concentration 35% by mass Thermosetting Resin BMI-4000 (bismaleimide) 35 (B) NC-3000H (epoxy resin) 15 NC-7000L (epoxy resin) 10 Polyaminobismaleimide Compound (B-1) solid concentration 70% by mass 50 Polyaminobismaleimide Compound (B-2) solid concentration 70% by mass Polyaminobismaleimide Compound (B-3) solid concentration 70% by mass Phenol-Modified Cyanate Prepolymer (B-4) solid concentration 70% by mass Styrenic Thermoplastic Tuftec H1043 0 0 0 0 Elastomer (C) Inorganic Filler (D) SC-2050 KNK solid concentration 70% by mass 82 68 62 93 Curing Accelerator (E) Perbutyl-P 0.7 0.7 G-8009L solid concentration 50% by mass 0.4 0.3 0.1 0.4 Manganese Naphthenate Flame Retardant (F) OP-935 12 10 10 12 HCA-HQ 8 7 7 8 Organic Solvent Toluene 32 20 Methyl ethyl ketone 8 3 Resin Composition Compatibility with solvent A A A A after solvent evaporation A A A A Prepreg Appearance A A A A Laminate Formability A A A A Dielectric Constant 10 GHz 3.8 3.8 3.9 3.8 Dielectric Dissipation Factor 10 GHz 0.0059 0.0057 0.0056 0.0058 Copper Foil Peel Strength (kN/m) 0.56 0.55 0.54 0.56 Soldering Heat Resistance ordinary state 3 3 3 3 after PCT-1 hr treatment 3 3 3 3 after PCT-3 hr treatment 3 3 3 3 after PCT-5 hr treatment 3 3 3 3 Glass Transition Temperature (° C.) 224 211 210 219 Thermal Expansion Coefficient (ppm/° C.) 41 42 44 40 Flame Retardancy V-0 V-0 V-0 V-0 Comparative Example 5 6 7 8 Polyphenylene Ether Polyphenylene Ether Derivative (A-1) solid concentration 35% by mass 100 100 100 Derivative (A) Polyphenylene Ether Derivative (A-2) solid concentration 35% by mass 100 Polyphenylene Ether Derivative (A-3) solid concentration 35% by mass Polyphenylene Ether Derivative (A-4) solid concentration 35% by mass Polyphenylene Ether Derivative (A-5) solid concentration 35% by mass Polyphenylene Ether Derivative (A-6) solid concentration 35% by mass Thermosetting Resin BMI-4000 (bismaleimide) (B) NC-3000H (epoxy resin) NC-7000L (epoxy resin) Polyaminobismaleimide Compound (B-1) solid concentration 70% by mass 50 Polyaminobismaleimide Compound (B-2) solid concentration 70% by mass 50 Polyaminobismaleimide Compound (B-3) solid concentration 70% by mass 50 Phenol-Modified Cyanate Prepolymer (B-4) solid concentration 70% by mass 33 Styrenic Thermoplastic Tuftec H1043 0 0 0 0 Elastomer (C) Inorganic Filler (D) SC-2050 KNK solid concentration 70% by mass 93 93 77 93 Curing Accelerator (E) Perbutyl-P 0.7 0.7 0.7 G-8009L solid concentration 50% by mass 0.4 0.4 0.1 0.4 Manganese Naphthenate 0.006 Flame Retardant (F) OP-935 12 12 12 12 HCA-HQ 8 8 7 8 Organic Solvent Toluene 20 20 9 20 Methyl ethyl ketone Resin Composition Compatibility with solvent A A A A after solvent evaporation A A A A Prepreg Appearance A A A A Laminate Formability A A A A Dielectric Constant 10 GHz 3.7 3.8 3.7 3.8 Dielectric Dissipation Factor 10 GHz 0.0058 0.0059 0.0058 0.0058 Copper Foil Peel Strength (kN/m) 0.54 0.55 0.53 0.57 Soldering Heat Resistance ordinary state 3 3 3 3 after PCT-1 hr treatment 3 3 3 3 after PCT-3 hr treatment 3 3 3 3 after PCT-5 hr treatment 3 3 3 3 Glass Transition Temperature (° C.) 223 224 221 213 Thermal Expansion Coefficient (ppm/° C.) 38 37 41 39 Flame Retardancy V-0 V-0 V-0 V-0 Comparative Example 9 10 11 12 Polyphenylene Ether Polyphenylene Ether Derivative (A-1) solid concentration 35% by mass Derivative (A) Polyphenylene Ether Derivative (A-2) solid concentration 35% by mass Polyphenylene Ether Derivative (A-3) solid concentration 35% by mass 100 Polyphenylene Ether Derivative (A-4) solid concentration 35% by mass 100 Polyphenylene Ether Derivative (A-5) solid concentration 35% by mass 100 Polyphenylene Ether Derivative (A-6) solid concentration 35% by mass 100 Thermosetting Resin BMI-4000 (bismaleimide) (B) NC-3000H (epoxy resin) NC-7000L (epoxy resin) Polyaminobismaleimide Compound (B-1) solid concentration 70% by mass 50 50 Polyaminobismaleimide Compound (B-2) solid concentration 70% by mass 50 Polyaminobismaleimide Compound (B-3) solid concentration 70% by mass 50 Phenol-Modified Cyanate Prepolymer (B-4) solid concentration 70% by mass Styrenic Thermoplastic Tuftec H1043 0 0 0 0 Elastomer (C) Inorganic Filler (D) SC-2050 KNK solid concentration 70% by mass 93 93 93 93 Curing Accelerator (E) Perbutyl-P 0.7 0.7 0.7 0.7 G-8009L solid concentration 50% by mass 0.4 0.4 0.4 0.4 Manganese Naphthenate Flame Retardant (F) OP-935 12 12 12 12 HCA-HQ 8 8 8 8 Organic Solvent Toluene 20 20 20 20 Methyl ethyl ketone Resin Composition Compatibility with solvent A A A A after solvent evaporation A A A A Prepreg Appearance A A A A Laminate Formability A A A A Dielectric Constant 10 GHz 3.8 3.7 3.8 3.7 Dielectric Dissipation Factor 10 GHz 0.0059 0.0058 0.0060 0.0059 Copper Foil Peel Strength (kN/m) 0.54 0.55 0.54 0.54 Soldering Heat Resistance ordinary state 3 3 3 3 after PCT-1 hr treatment 3 3 3 3 after PCT-3 hr treatment 3 3 3 3 after PCT-5 hr treatment 3 3 3 3 Glass Transition Temperature (° C.) 218 212 224 221 Thermal Expansion Coefficient (ppm/° C.) 41 39 41 43 Flame Retardancy V-0 V-0 V-0 V-0 (The unit of content is part by mass. For solution, the content is in terms of solid content.) -
TABLE 7 Comparative Example 13 14 15 16 Polyphenylene Ether Polyphenylene Ether Derivative (A-1) solid concentration 35% by mass 100 100 100 100 Derivative (A) Thermosetting Resin (B) Polyaminobismaleimide Compound (B-1) solid concentration 70% by mass 122 50 125 100 Non-styrenic TOPAS 8007 51 47 53 245 Thermoplastic Elastomer TOPAS 6017 Inorganic Filler (D) SC-2050 KNK solid concentration 70% by mass 98 62 100 179 Curing Accelerator (E) Perbutyl-P 1.7 0.3 0.2 0.7 G-8009L solid concentration 50% by mass 0.9 0.2 0.1 0.4 Flame Retardant (F) OP-935 14 9 14 26 HCA-HQ 10 6 10 18 Organic Solvent Toluene 46 18 47 197 Methyl ethyl ketone Resin Composition Compatibility with solvent A C C C after solvent evaporation C C C C Prepreg Appearance C C C C Laminate Formability C C C C Dielectric Constant 10 GHz 3.6 3.8 3.9 3.8 Dielectric Dissipation Factor 10 GHz 0.0050 0.0049 0.0052 0.0048 Copper Foil Peel Strength (kN/m) 0.49 0.41 0.43 0.42 Soldering Heat Resistance ordinary state 3 3 3 3 after PCT-1 hr treatment 3 3 3 3 after PCT-3 hr treatment 3 3 3 3 after PCT-5 hr treatment 3 3 3 3 Glass Transition Temperature (° C.) 211 209 210 192 Thermal Expansion Coefficient (ppm/° C.) 44 44 48 51 Flame Retardancy V-0 V-1 V-0 V-1 Comparative Example 17 18 19 20 Polyphenylene Ether Polyphenylene Ether Derivative (A-1) solid concentration 35% by mass 100 100 100 100 Derivative (A) Thermosetting Resin (B) Polyaminobismaleimide Compound (B-1) solid concentration 70% by mass 50 50 125 100 Non-styrenic TOPAS 8007 Thermoplastic Elastomer TOPAS 6017 51 47 53 245 Inorganic Filler (D) SC-2050 KNK solid concentration 70% by mass 100 62 100 179 Curing Accelerator (E) Perbutyl-P 0.7 0.7 0.5 0.7 G-8009L solid concentration 50% by mass 0.4 0.4 0.2 0.4 Flame Retardant (F) OP-935 14 9 14 26 HCA-HQ 10 6 10 18 Organic Solvent Toluene 85 66 100 442 Methyl ethyl ketone Resin Composition Compatibility with solvent C C C C after solvent evaporation C C C C Prepreg Appearance C C C C Laminate Formability C C C C Dielectric Constant 10 GHz 3.7 3.8 3.7 3.8 Dielectric Dissipation Factor 10 GHz 0.0051 0.0052 0.0051 0.0048 Copper Foil Peel Strength (kN/m) 0.48 0.47 0.49 0.47 Soldering Heat Resistance ordinary state 3 3 3 3 after PCT-1 hr treatment 3 3 3 3 after PCT-3 hr treatment 3 3 3 3 after PCT-5 hr treatment 3 3 3 3 Glass Transition Temperature (° C.) 211 204 208 193 Thermal Expansion Coefficient (ppm/° C.) 38 47 47 53 Flame Retardancy V-0 V-0 V-0 V-0 (The unit of content is part by mass. For solution, the content is in terms of solid content.) - Abbreviations of the materials in Tables 3 to 7 are as follows.
- BMI-4000: 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane (trade name, manufactured by Daiwa Kasei Industry Co., Ltd.)
- NC-3000H: biphenylaralkyl-type epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd.)
- NC-7000L: naphthol novolak-type epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd.)
- Tuftec (registered trademark) H1043: SEBS, styrene content=67% by mass (manufactured by Asahi Kasei Chemicals Corporation)
- Tuftec (registered trademark) H1051: SEBS, styrene content=42% by mass (manufactured by Asahi Kasei Chemicals Corporation)
- Tuftec (registered trademark) H1053: SEBS, styrene content=29% by mass (manufactured by Asahi Kasei Chemicals Corporation)
- Tuftec (registered trademark) H1052: SEBS, styrene content=20% by mass (manufactured by Asahi Kasei Chemicals Corporation)
- Tuftec (registered trademark) H1221: SEBS, styrene content=12% by mass (manufactured by Asahi Kasei Chemicals Corporation)
- Tuftec (registered trademark) M1911: SEBS, styrene content=30% by mass (manufactured by Asahi Kasei Chemicals Corporation)
- Tuftec (registered trademark) M1913: SEBS, styrene content=20% by mass (manufactured by Asahi Kasei Chemicals Corporation)
- Tuftec (registered trademark) P2000: SBBS, styrene content=67% by mass (manufactured by Asahi Kasei Chemicals Corporation)
- Septon (registered trademark) 2002: SEPS, styrene content=30% by mass (manufactured by Kuraray Co., Ltd.)
- Septon (registered trademark) 2005: SEPS, styrene content=20% by mass (manufactured by Kuraray Co., Ltd.)
- SMA (registered trademark) Resin EF-30 (manufactured by Cray Valley Technologies USA) (styrene content=75% by mass)
- SMA (registered trademark) Resin EF-80 (manufactured by Cray Valley Technologies USA) (styrene content=89% by mass)
- TOPAS (registered trademark) 8007: cycloolefin copolymer (norbornene-derived structural unit content=64%) (manufactured by Topas Advanced Polymers)
- TOPAS (registered trademark) 6017: cycloolefin copolymer (norbornene-derived structural unit content=82%) (manufactured by Topas Advanced Polymers)
- SC-2050 KNK: spherical molten silica, mean particle size=0.5 μm, surface treatment: vinylsilane coupling agent (1% by mass/solid content), dispersant: methyl isobutyl ketone, solid concentration 70% by mass, density 2.2 g/cm3 (trade name, manufactured by Admatechs Company Limited)
- Perbutyl (registered trademark) P: α,α′-bis(t-butylperoxy)diisopropylbenzene (trade name, manufactured by NOF Corp.)
- G-8009L: isocyanate-masked imidazole (addition product of hexamethylene-diisocyanate resin and 2-ethyl-4-methylimidazole) (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
- Manganese naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.)
- OP-935: aluminum dialkylphosphinate, metal salt of disubstituted phosphinic acid, phosphorus content: 23.5% by mass (trade name, manufactured by Clariant Corp.)
- HCA-HQ: 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, cyclic organic phosphorus compound, phosphorus content: 9.6% by mass (manufactured by Sanko Co., Ltd.)
- As obvious from the results shown in Tables 3 to 5, Examples of the present invention are excellent in compatibility of the resin compositions and appearance of the prepregs, and the copper-clad laminates produced using these are good and well-balanced in all the formability, the high frequency properties (dielectric properties), the adhesion to conductor, the soldering heat resistance, the glass transition temperature, the thermal expansion coefficient and the flame retardancy.
- On the other hand, as obvious from the results in Tables 6 and 7, in Comparative Examples, some resin compositions and prepregs are not good in compatibility and appearance (Comparative Examples 13 to 20). In addition, the copper-clad laminates of Comparative Examples are inferior to those of Examples in point of any of formability, dielectric properties, adhesion to conductor, soldering heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy.
- Using a specific thermosetting resin composition along with a polyphenylene ether derivative having a specific structure and a styrenic thermoplastic elastomer, a resin composition having good compatibility, especially excellent high frequency properties (low dielectric constant, low dielectric dissipation factor), high adhesion to conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient and high flame retardancy can be obtained.
- In addition, for the resin composition of the present invention, the material cost and the production cost for substrate material can be suppressed, and the working environment is excellent, and therefore, the prepreg and the laminate to be provided using the resin composition can be favorably used for use for electronic parts such as multilayer printed wiring boards, etc.
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US11041045B2 (en) | 2021-06-22 |
CN107531991A (en) | 2018-01-02 |
CN107531991B (en) | 2020-08-04 |
EP3290480B1 (en) | 2020-12-09 |
KR102466876B1 (en) | 2022-11-11 |
WO2016175326A1 (en) | 2016-11-03 |
EP3290480A4 (en) | 2019-01-09 |
TWI706993B (en) | 2020-10-11 |
SG11201708802VA (en) | 2017-11-29 |
EP3290480A1 (en) | 2018-03-07 |
KR20170141687A (en) | 2017-12-26 |
JPWO2016175326A1 (en) | 2018-02-22 |
JP6705447B2 (en) | 2020-06-03 |
TW201702311A (en) | 2017-01-16 |
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